Aqueous dispersions

ABSTRACT

Aqueous dispersions of cationic water-soluble polymers are provided, as well as processes for making and methods of using the same.

This application is a continuation-in-part of U.S. application Ser. No.08/725,325, filed Oct. 3, 1996, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to aqueous dispersions comprised of water-solublepolymers, processes for making said dispersions, and methods of usingsaid dispersions in water treating, dewatering, water clarification,papermaking, oil field, soil conditioning, food processing, mineralprocessing, and biotechnological applications.

U.S. Pat. No. 4,380,600 discloses a process for producing an aqueousdispersion of water-soluble polymers. The aqueous dispersion may containinorganic salt. However, the aqueous dispersions exemplified thereinhave disadvantageously high bulk viscosities.

U.S. Pat. No. 4,673,704 and EP 0 170 394 A2 disclose products comprisedof particles above 20 microns in size of a high molecular weight polymergel interconnected by a continuous phase that is an aqueous solution ofan equilibrating agent that holds the water content of the particles inequilibrium with the water content of the aqueous phase and thatprevents substantial agglomeration of the particles in the fluidproduct. Although these references are entitled “Aqueous PolymerDispersions,” the products disclosed therein are distinguished from theaqueous dispersions of U.S. Pat. No. 4,380,600 and from the aqueousdispersions of the instant invention in that the particles of U.S. Pat.No. 4,673,704 and EP 0 170 394 A2 are not generally held suspended in acontinuous matrix of the aqueous phase but instead generally restsubstantially in contact with one another but slide over one another. Aprocess for dispersing the polymer gel into an aqueous solution of anequilibrating agent and working the polymer while in that medium isdisclosed in U.S. Pat. No. 4,778,836 and EP 0 169 674 B1. Also, U.S.Pat. No. 4,522,968 discloses a process for dispersing certain powderedwater-soluble homopolymers or copolymers in an aqueous solutioncontaining a polymer of ethylene oxide and/or propylene oxide.

U.S. Pat. Nos. 4,929,655 and 5,006,590 disclose processes for preparingaqueous dispersions of water-soluble polymers by polymerizingbenzyl-containing monomers in the presence of an organic high molecularmultivalent cation and a multivalent anionic salt. The benzylgroup-containing monomer may be replaced by a hydrophobic alkylgroup-containing monomer as in EP 0 525 751. Numerous references concernthese and similar polymers, e.g. U.S. Pat. Nos. 5,332,506; 5,332,507;5,330,650; 5,292,793, 5,435,922; 5,466,338; EP 0 595 156 A1; EP 0 630909 A1; EP 0 657 478 A2; EP 0 629 583 A2; EP 0 617 991 A1, EP 0 183 466B1, EP 0 637 598 A2; EP 0 717 056 A2; JP 61-6396; JP 61-6397; JP61-6398; JP 62-262799; JP 64-15130; JP 2-38131; JP 62 15251; JP61-138607; Hei 6-329866; and JP 62-100548. Although some of the aqueousdispersions in these references have relatively low bulk viscosities,the need to include special monomers containing aromatic or hydrophobicalkyl groups in order to render the polymer insoluble in salt solutionmay be disadvantageous because the special monomers may be expensive anddilutive of the polymer effect in a specific application.

The effect of salts on the solubility of various substances in aqueoussolution is well discussed in the scientific literature. The“Hofmeister” series ranks anions according to their ability to increaseor decrease the solubility of substances in water. Although positions inthe ranking may vary slightly, depending on the substance, a generallyaccepted ranking of the anions is:

Salting-out SO₄ ²⁻ ˜ HPO₄ ²⁻ > F⁻ > Cl⁻ > Br⁻ > I⁻ ˜ ClO₄ ⁻ > SCN⁻Salting-in (kosmotropic) (chaotropic)

Kosmotropic salts generally decrease the solubility of substances inwater. For instance, the Hofmeister ranking apparently guided the choiceof salts for precipitating cationic water soluble polymers, containinghydrophobic groups, in U.S. Pat. Nos. 4,929,655 and 5,006,590, as wellas EP 0 630 909 A1, EP 0 525 751 A1, and EP 0 657 478 A2, as evidencedby their use of strongly kosmotropic salts containing sulfate andphosphate anions. On the other hand, chaotropic salts generally increasethe solubility of substances in water.

There are numerous means known to those skilled in the art fordetermining whether a particular salt is kosmotropic or chaotropic.Representative salts which contain anions such as sulfate, fluoride,phosphate, acetate, citrate, tartrate and hydrogenphosphate arekosmotropic. Representative salts which contain anions such asthiocyanate, perchlorate, chlorate, bromate, iodide, nitrate and bromideare chaotropic. The chloride anion is generally considered to be atabout the middle of the Hofmeister ranking, being either weaklychaotropic or weakly kosmotropic, depending on the particular system. Inthe instant invention, although occasionally chaotropic, inorganic saltswhich contain the chloride anion tend to be kosmotropic.

Small amounts of sodium thiocyanate, for instance about 0.1% by weight,on total, have been reported to be useful as stabilizers for polymerdispersions as in EP 0 657 478 A2, where (NH₄)₂SO₄ was used to depositthe polymer. Sodium thiocyanate and sodium iodide have been reported tobe useful as stabilizers for hydroxylamine-containing water-solublepolymer systems, as in EP 0 514 649 A1. U.S. Pat. No. 3,234,163 teachesthat small amounts of thiocyanate salts, preferably 0.1 to 1 percent,based on the weight of the polymer, are useful for stabilizingpolyacrylamide solutions.

The Hofmeister ranking has been observed in solutions of high molecularweight, water-soluble polymers. For instance, the effect of varioussalts on the solubility of synthetic, water-soluble polymers wasexplored by Shuji Saito, J. Polym. Sci.: Pt. A, Vol. 7, pp. 1789-1802(1969). This author discussed the effect of various anions on polymersolubility and stated “This anionic order seems to be independent of thetype of counter cations and is in line with Hofmeister's lyotropicseries for anions.” Similarly, in M. Leca, Polymer Bulletin, Vol. 16,pp. 537-543, 1986, the viscosity of polyacrylamide, as determined in 1Nsolutions of various salts, was found to increase in the order HPO₄²⁻<H₂O<Br⁻<NO₃ ⁻<I⁻=BrO₃ ⁻<ClO₃ ⁻=SCN⁻. The viscosities were reported tobe higher in more chaotropic salt solutions than in less chaotropic, orkosmotropic, salt solutions. Certain novel cationic polyelectrolytes,termed ionene polymers, were reported (D. Casson and A. Rembaum,Macromolecules, Vol. 5, No. 1, 1972, pp. 75-81) to be insoluble ineither 0.4 M potassium iodide or 0.4 M potassium thiocyanate. It hasalso been reported (W-F. Lee and C-C. Tsai, J. Appl. Polym. Sci., Vol.52, pp. 1447-1458, 1994) that poly(trimethyl acrylamido propyl ammoniumiodide) did not dissolve in 0.5 M Na₂ClO₄ or 0.5 M NaNO₃.

Certain anionic organic salts, such as hydrotropes and surfactants, alsotend to increase the solubility of substances in water. However,poly(allylammonium chloride) was reported (T. Itaya et al., J. Polym.Sci., Pt. B: Polym. Phys., Vol. 32, pp. 171-177, 1994, and references 3,5 and 6 therein; also Macromolecules, Vol 26, pp. 6021-6026, 1993) toprecipitate in solutions containing the sodium salt ofp-ethylbenzenesulfonate, p-propylbenzenesulfonate ornaphthalenesulfonate. Poly(4-vinyl pyridine) quaternized with butylchloride and poly(allylammonium chloride) were reported (M. Satoh, E.Yoda, and J. Komiyama, Macromolecules, Vol. 24, pp. 1123-27, 1991) toprecipitate in solutions of NaI and also in solutions containing thesodium salt of p-ethylbenzenesulfonate, respectively. Compositionscomprising sulphonated hydrocarbon surfactants and hydrophilic cationicpolymers were disclosed in U.S. Pat. No. 5,130,358. Mixtures ofchaotropic salts, or anionic organic salts, and kosmotropic salts may beused to precipitate cationic polymers as in U.S. application Ser. No.08/725,436, filed even date herewith.

Aqueous dispersions of water-soluble polymers are disclosed in U.S. Pat.Nos. 5,403,883; 5,480,934; 5,541,252; EP 0 624 617 A1; EP 0 573 793 A1;and WO 95/11269. A problem remains in that the aqueous dispersionsexemplified in these references still have relatively high bulkviscosities.

A process for preparing crosslinked copolymer beads from water-solublemonomers in an aqueous solution containing an inorganic salt and adispersant is disclosed in U.S. Pat. No. 5,498,678 and EP 0 604 109 A2.Mixtures of aqueous dispersions and water-in-oil emulsions are disclosedin Hei 7-62254 and Hei 6-25540. The addition of a nonionic surfactantand an oleaginous liquid to an aqueous dispersion to maintainflowability is disclosed in U.S. Pat. No. 5,045,587. Mixtures ofcationic polymers are disclosed in Sho-52-71392 and homogeneous blendsof water-soluble polymers are disclosed in U.S. Pat. No. 4,835,206 andEP 0 262 945 B1. Bimodal cationics for water clarification are disclosedin U.S. Patent Nos. 4,588,508 and 4,699,951. Blends of water-in-oilpolymer emulsions are disclosed in U.S. patent application Ser. No.08/408,743.

In spite of the effort to make satisfactory aqueous dispersions, theproblem remains of producing aqueous dispersions of high molecularweight water soluble polymers that have advantageously low bulkviscosities, high active solids content, minimal quantities of dilutivematerial, and that dissolve readily and can be prepared with a broadrange of cationicity.

SUMMARY OF THE INVENTION

This problem is solved in the present invention by providing novelaqueous dispersions of high molecular weight water-soluble orwater-swellable polymers, as well as processes for making and methods ofusing said aqueous dispersions. Accordingly, an aqueous dispersion ofpolymers is provided which comprises: (a) a first cationic water-solubleor water-swellable polymer; and (b) at least one second water-solublepolymer different from said first polymer; and (c) a kosmotropic salt;and (d) a chaotropic salt, wherein the amounts of said (b), (c) and (d)are such that a homogeneous composition is obtained in the absence ofsaid (b). In another embodiment, an aqueous dispersion of polymers isprovided which comprises: (a) a first cationic water-soluble orwater-swellable polymer; and (b) at least one second water-solublepolymer different from said first polymer; and (c) a kosmotropic salt;and (d) an anionic organic salt, wherein the amounts of said (b), (c)and (d) are such that a homogeneous composition is obtained in theabsence of said (b).

In another embodiment, an aqueous dispersion of polymers is providedwhich is comprised of (a) a discontinuous phase containing polymer thatis comprised predominately of a first cationic water-soluble orwater-swellable polymer having at least one first recurring unit of theformula (I),

wherein R₁ is H or CH₃, A is O or NH, B is an alkylene or branchedalkylene or oxyalkylene group having from 1 to 5 carbons, R₂ is amethyl, ethyl, or propyl group, R₃ is a methyl, ethyl, or propyl group,R₄ is a methyl, ethyl or propyl group, and X is a counterion; and (b) atleast one second water-soluble polymer different from said firstpolymer; wherein, if said first polymer is further comprised of a secondrecurring unit of formula (I) wherein R₁ is H or CH₃, A is O or NH, B isan alkylene or branched alkylene or oxyalkylene group having from 1 to 5carbons, X is a counterion, and R₂, R₃ or R₄ is selected from the groupconsisting of C₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅, then the amount ofsaid first recurring unit is greater than the amount of said secondrecurring unit on a molar basis, and wherein, if said R₂, R₃ and R₄ insaid first recurring unit together contain a total of 3 carbon atoms,then said first polymer is devoid of hydrophobic recurring units.

In another embodiment, an aqueous dispersion of polymers is providedwhich comprises: (a) a first cationic water-soluble or water-swellablepolymer having at least one recurring unit of the formula (I), whereinR₁ is H or CH₃, A is O or NH, B is an alkylene or branched alkylene oroxyalkylene group having from 1 to 5 carbons, R₂ is a methyl, ethyl, orpropyl group, R₃ is a methyl, ethyl, or propyl group, R₄ is an alkyl orsubstituted alkyl group having from 1 to 10 carbons, or an aryl orsubstituted aryl group having from 6 to 10 carbons, X is a counterion,and R₂, R₃, and R₄ together contain a total of at least 4 carbon atoms;and (b) at least one second water-soluble polymer different from saidfirst polymer, wherein a homogeneous composition is obtained in theabsence of said (b).

In another embodiment, a process for making an aqueous dispersion ofpolymers is provided which comprises polymerizing vinyl-additionmonomers to form an aqueous dispersion comprised of a first cationicwater-soluble or water-swellable polymer, wherein said polymerizing iscarried out in the presence of an aqueous composition comprised of (a)at least one second water-soluble polymer different from said firstpolymer; (b) a kosmotropic salt; and (c) a chaotropic salt, wherein theamounts of said (a), (b) and (c) are such that a homogeneous compositionis obtained if said polymerizing is carried out in the absence of said(a).

In another embodiment, a process for making an aqueous dispersion ofpolymers is provided which comprises polymerizing vinyl-additionmonomers to form an aqueous dispersion comprised of a first cationicwater-soluble or water-swellable polymer, wherein said polymerizing iscarried out in the presence of an aqueous composition comprised of (a)at least one second water-soluble polymer different from said firstpolymer; (b) a kosmotropic salt; and (c) of an anionic organic salt,wherein the amounts of said (a), (b) and (c) are such that a homogeneouscomposition is obtained if said polymerizing is carried out in theabsence of said (a).

In another embodiment, a process for making an aqueous dispersion ofpolymers is provided which comprises polymerizing vinyl-additionmonomers comprised of at least one monomer of the formula (II)

to form an aqueous dispersion comprised of a first cationicwater-soluble or water-swellable polymer, wherein R₁ is H or CH₃, A is Oor NH, B is an alkylene or branched alkylene or oxyalkylene group havingfrom 1 to 5 carbons, R₂ is a methyl, ethyl, or propyl group, R₃ is amethyl, ethyl, or propyl group, R₄ is a methyl, ethyl or propyl group,and X is a counterion; wherein said polymerizing is carried out in thepresence of an aqueous composition comprised of at least one secondwater-soluble polymer different from said first polymer; wherein, ifsaid vinyl-addition monomers are further comprised of a second monomerof formula (II) wherein R₁ is H or CH₃, A is O or NH, B is an alkyleneor branched alkylene or oxyalkylene group having from 1 to 5 carbons, Xis a counterion, and R₂, R₃ or R₄ is selected from the group consistingof C₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅, then the amount of said firstmonomer is greater than the amount of said second monomer on a molarbasis, and wherein, if said R₂, R₃ and R₄ in said first monomer togethercontain a total of 3 carbon atoms, then said first polymer is devoid ofhydrophobic recurring units.

In another embodiment, a process for making an aqueous dispersion ofpolymers is provided which comprises polymerizing vinyl-additionmonomers comprised of at least one monomer of the formula (II) to forman aqueous dispersion comprised of a first water-soluble orwater-swellable cationic polymer, wherein R₁ is H or CH₃, A is O or NH,B is an alkylene or branched alkylene or oxyalkylene group having from 1to 5 carbons, R₂ is a methyl, ethyl, or propyl group, R₃ is a methyl,ethyl, or propyl group, R₄ is an alkyl or substituted alkyl group havingfrom 1 to 10 carbons, or an aryl or substituted aryl group having from 6to 10 carbons, X is a counterion, and R₂, R₃, and R₄ together contain atotal of at least 4 carbon atoms; and wherein said polymerizing iscarried out in the presence of an aqueous composition comprised of anamount of at least one second water-soluble polymer different from saidfirst polymer; and wherein said amount of said second polymer is suchthat a homogeneous composition is obtained if said polymerizing iscarried out in the absence of said second polymer.

In another embodiment, a process for blending two or more aqueousdispersions is provided, comprising intermixing (a) a first aqueousdispersion of a water-soluble or water-swellable polymer with (b) asecond aqueous dispersion of a water-soluble or water-swellable polymer,wherein said (a) is different from said (b), to form a third aqueousdispersion.

In another embodiment, a method of dewatering a suspension of dispersedsolids is provided which (a) intermixing an aqueous dispersion ofpolymers, or aqueous admixture thereof, in an amount effective fordewatering, with a suspension of dispersed solids, and (b) dewateringsaid suspension of dispersed solids, said aqueous dispersion beingcomprised of (i) a first cationic water-soluble or water-swellablepolymer; and (ii) at least one second water-soluble polymer differentfrom said first polymer; and (iii) a kosmotropic salt; and (iv) achaotropic salt, wherein the amounts of said (ii), (iii) and (iv) aresuch that a homogeneous composition is obtained in the absence of said(ii).

In another embodiment, a method of dewatering a suspension of dispersedsolids is provided which comprises (a) intermixing an aqueous dispersionof polymers, or aqueous admixture thereof, in an amount effective fordewatering, with a suspension of dispersed solids, and (b) dewateringsaid suspension of dispersed solids, said aqueous dispersion beingcomprised of (i) a first cationic water-soluble or water-swellablepolymer; and (ii) at least one second water-soluble polymer differentfrom said first polymer; and (iii) a kosmotropic salt; and (iv) ananionic organic salt, wherein the amounts of said (ii), (iii) and (iv)are such that a homogeneous composition is obtained in the absence ofsaid (ii).

In another embodiment, a method of dewatering a suspension of dispersedsolids is provided which comprises (a) intermixing an aqueous dispersionof polymers, or aqueous admixture thereof, in an amount effective fordewatering, with a suspension of dispersed solids, and (b) dewateringsaid suspension of dispersed solids, said aqueous dispersion beingcomprised of (i) a discontinuous phase containing polymer that iscomprised predominately of a first cationic water-soluble orwater-swellable polymer having at least one first recurring unit of theformula (I), wherein R₁ is H or CH₃, A is O or NH, B is an alkylene orbranched alkylene or oxyalkylene group having from 1 to 5 carbons, R₂ isa methyl, ethyl, or propyl group, R₃ is a methyl, ethyl, or propylgroup, R₄ is a methyl, ethyl or propyl group, and X is a counterion;(ii) at least one second water-soluble polymer different from said firstpolymer; wherein, if said first polymer is further comprised of a secondrecurring unit of formula (I) wherein R₁ is H or CH₃, A is O or NH, B isan alkylene or branched alkylene or oxyalkylene group having from 1 to 5carbons, X is a counterion, and R₂, R₃ or R₄ is selected from the groupconsisting of C₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅, then the amount ofsaid first recurring unit is greater than the amount of said secondrecurring unit on a molar basis, and wherein, if said R₂, R₃ and R₄ insaid first recurring unit together contain a total of 3 carbon atoms,then said first polymer is devoid of hydrophobic recurring units.

In another embodiment, a method of dewatering a suspension of dispersedsolids is provided which comprises (a) intermixing an aqueous dispersionof polymers, or aqueous admixture thereof, in an amount effective fordewatering, with a suspension of dispersed solids, and (b) dewateringsaid suspension of dispersed solids, said aqueous dispersion beingcomprised of (i) a first cationic water-soluble or water-swellablepolymer having at least one recurring unit of the formula (I), whereinR₁ is H or CH₃, A is O or NH, B is an alkylene or branched alkylene oroxyalkylene group having from 1 to 5 carbons, R₂ is a methyl, ethyl, orpropyl group, R₃ is a methyl, ethyl, or propyl group, R₄ is an alkyl orsubstituted alkyl group having from 1 to 10 carbons, or an aryl orsubstituted aryl group having from 6 to 10 carbons, X is a counterion,and R₂, R₃, and R₄ together contain a total of at least 4 carbon atoms;and (ii) at least one second water-soluble polymer different from saidfirst polymer, wherein a homogeneous composition is obtained in theabsence of said (ii).

In another embodiment, a process for producing substantially drywater-soluble or water-swellable vinyl-addition polymer particles isprovided which comprises (a) spray-drying a vinyl-additionpolymer-containing aqueous dispersion into a gas stream with a residencetime of about 8 to about 120 seconds and at an outlet temperature ofabout 70° C. to about 150° C. and (b) collecting resultant polymerparticles.

In another embodiment, substantially dry water-soluble orwater-swellable polymer particles are provided which are comprised of(a) a first cationic water-soluble or water-swellable polymer; and (b)at least one second water-soluble polymer different from said firstpolymer; and (c) a kosmotropic salt; and (d) a chaotropic salt, whereinabout 90% or more of said polymer particles each individually containsboth said (a) and said (b), said particles having a bulk density ofabout 0.4 grams per cubic centimeter to about 1.0 grams per cubiccentimeter.

In another embodiment, there is provided a method comprising (a)intermixing a composition comprising substantially dry water-soluble orwater-swellable polymer particles comprised of (i) a first cationicwater-soluble or water-swellable polymer; and (ii) at least one secondwater-soluble polymer different from said first polymer; and (iii) akosmotropic salt; and (iv) a chaotropic salt, wherein about 90% or moreof said polymer particles each individually contains both said (i) andsaid (ii), said particles having a bulk density of about 0.4 grams percubic centimeter to about 1.0 grams per cubic centimeter, with water toform an aqueous polymer admixture, (b) intermixing said aqueous polymeradmixture, in an amount effective for dewatering, with a suspension ofdispersed solids, and (c) dewatering said suspension of dispersedsolids.

In another embodiment, there is provided a method comprising (a)intermixing a composition comprising substantially dry water-soluble orwater-swellable polymer particles comprised of (i) a first cationicwater-soluble or water-swellable polymer; and (ii) at least one secondwater-soluble polymer different from said first polymer; and (iii) akosmotropic salt; and (iv) an anionic organic salt, wherein about 90% ormore of said polymer particles each individually contains both said (i)and said (ii), said particles having a bulk density of about 0.4 gramsper cubic centimeter to about 1.0 grams per cubic centimeter, with waterto form an aqueous polymer admixture, (b) intermixing said aqueouspolymer admixture, in an amount effective for dewatering, with asuspension of dispersed solids, and (c) dewatering said suspension ofdispersed solids.

In another embodiment, there is provided a method comprising (a)intermixing a composition comprising substantially dry water-soluble orwater-swellable polymer particles comprised of (i) a first cationicwater-soluble or water-swellable polymer having at least one recurringunit of the formula (I), wherein R₁ is H or CH₃, A is O or NH, B is analkylene or branched alkylene or oxyalkylene group having from 1 to 5carbons, R₂ is a methyl, ethyl, or propyl group, R₃ is a methyl, ethyl,or propyl group, R₄ is an alkyl or substituted alkyl group having from 1to 10 carbons, or an aryl or substituted aryl group having from 6 to 10carbons, X is a counterion, and R₂, R₃, and R₄ together contain a totalof at least 4 carbon atoms; and (ii) at least one second water-solublepolymer different from said first polymer, wherein about 90% or more ofsaid polymer particles each individually contains both said (i) and said(ii), said particles having a bulk density of about 0.4 grams per cubiccentimeter to about 1.0 grams per cubic centimeter, with water to forman aqueous polymer admixture, (b) intermixing said aqueous polymeradmixture, in an amount effective for dewatering, with a suspension ofdispersed solids, and (c) dewatering said suspension of dispersedsolids.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The aqueous dispersions of the instant invention contain a firstcationic water-soluble or water-swellable polymer, preferably avinyl-addition polymer. The cationic charge of said first cationicpolymer may vary over a broad range by containing from about 1% to about100% cationic recurring units, preferably about 5% or greater, morepreferably about 10% or greater, even more preferably about 20% orgreater, most preferably about 30% or greater, preferably about 90% orless, more preferably about 80% or less, most preferably about 70% orless, by mole based on total moles of recurring units in said firstcationic polymer. Cationic recurring units may be formed bypost-reaction of polymer, but are preferably formed by polymerization ofcationic monomers. Cationic monomers may include any cationic monomer,including diallyldialkylammonium halide, cationic (meth)acrylates, andcationic (meth)acrylamides commonly used in preparing water-solublepolymers, preferably diallyldimethylammonium halide, as well as acid andquaternary salts of dialkylaminoalkyl(alk)acrylate anddialkylaminoalkyl(alk)acrylamide. Cationic recurring units may be formedby the polymerization of quaternizable monomers such asdialkylaminoalkyl(alk)acrylate or dialkylaminoalkyl(alk)acrylamide,followed by acidification or quaternization. Most preferably, the firstcationic polymer contains cationic recurring units of the formula (I),preferably formed by polymerization of the corresponding monomers of theformula (II):

wherein R₁ is H or CH₃, A is O or NH, B is alkylene or branched alkyleneor oxyalkylene having from 1 to 5 carbons, R₂ and R₃ are eachindividually methyl, ethyl, or propyl, R₄ is an alkyl or substitutedalkyl group having from 1 to 10 carbon atoms, or an aryl or substitutedaryl group having from 6 to 10 carbon atoms, and X is a counterion.Preferably, R₂, R₃ and R₄ together contain at least a total of 4 carbonatoms, more preferably at least 5 carbon atoms. In certain preferredembodiments, R₄ is a methyl, ethyl or propyl group. In other preferredembodiments, R₄ is an alkyl or substituted alkyl group having from 4 to10 carbon atoms. In other preferred embodiments, R₄ is benzyl.Preferably, X is chloride, bromide, iodide, methylsulfate, orethylsulfate.

Monomers which may be copolymerized with the cationic monomers mentionedabove may be cationic, nonionic or anionic. Cationic monomers includethe monomers corresponding to (I) and other cationic monomers such asdiallydimethylammonium chloride, diallydiethylammonium chloride, etc.Nonionic monomers may include substantially water-soluble monomers suchas acrylamide, methacrylamide, and N-isopropylacrylamide, or monomerswhich are sparingly soluble in water such as t-butylacrylamide,N,N-dialkylacrylamide, diacetone acrylamide, ethyl acrylate, methylmethacrylate, methyl acrylate, styrene, butadiene, ethyl methacrylate,acrylonitrile, etc. and the like. Nonionic monomers may also includemonomers which become charged at low pH, such asdimethylaminoethylacrylate, dimethylaminoethylmethacrylate,diethylaminoethylacrylate, diethylaminoethylmethacrylate andcorresponding acrylamide derivatives such asmethacrylamidopropyldimethylamine. Preferred nonionic monomers areacrylamide, t-butyl acrylamide, methacrylamide, methyl methacrylate,ethyl acrylate and styrene. Anionic monomers may include acrylic acid,2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, theirsalts and the like. On a mole basis, the polymer contains fewer anionicrecurring units than cationic recurring units so that the polymer,although ampholytic, retains a net positive cationic charge. Preferably,the polymer contains less than 10 mole % anionic recurring units, basedon the total number of recurring units in the polymer.

The first cationic water-soluble or water-swellable polymer may be acopolymer and may contain other cationic recurring units or nonionicrecurring units. Nonionic recurring units may be formed fromwater-soluble monomers such as N-vinylpyridine, N-vinylpyrrolidone,hydroxyalkyl(meth)acrylates, etc., preferably (meth)acrylamide, or maybe formed from hydrophobic monomers having low water-solubility, so longas the inclusion of the poorly water-soluble, e.g. hydrophobic,recurring units does not render the resulting polymer water-insoluble orwater-nonswellable. The first cationic polymer may contain amounts ofrecurring units of water-soluble non-ionic monomers ranging from 0% toabout 99%, preferably about 10% or greater, more preferably about 20% orgreater, most preferably about 30% or greater; preferably about 90% orless, more preferably about 80% or less, most preferably about 70% orless, by mole based on total moles of recurring units in said polymer.The hydrophobic monomers may be hydrocarbon monomers e.g. styrene,butadiene, 1-alkene, vinyl cyclohexane, etc., other vinyl monomers suchas vinyl halide, other primarily aliphatic or aromatic compounds withpolymerizable double bonds, or monomers with only moderatewater-solubility such as acrylonitrile. Preferably, the hydrophobicmonomers are alkyl (alk)acrylates or aryl (alk)acrylates in which thealkyl or aryl groups contain about 1-12 carbon atoms, such as methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, hexyl (meth)acrylate, ethylhexyl (meth)acrylate,isoalkyl (meth)acrylate, cyclohexyl (meth)acrylate, or aromatic(meth)acrylate, or alkyl or aryl (alk)acrylamides in which the alkyl oraryl groups contain about 1-12 carbon atoms, such as methyl(meth)acrylamide, ethyl (meth)acrylamide, t-butyl (meth)acrylamide,dimethyl (meth)acrylamide, hexyl (meth)acrylamide, ethylhexyl(meth)acrylamide, isoalkyl (meth)acrylamide, cyclohexyl(meth)acrylamide, or aromatic (meth)acrylamide. The first cationicwater-soluble or water-swellable polymer may contain amounts ofhydrophobic non-ionic recurring units ranging from 0% to about 15%,preferably about 2% to about 10%, by mole based on total moles ofrecurring units in said polymer. Although hydrophobic recurring unitsmay be dilutive of the polymer effect in certain applications, inclusionin controlled amounts may advantageously affect a particularcharacteristic of the aqueous dispersion, e.g. solubility rate, bulkviscosity, cost, ease of processing, performance, etc. Depending on thespecific embodiment, it may be preferable for the polymer to be devoidof hydrophobic recurring units, or to contain chosen amounts ofhydrophobic recurring units so as to achieve an advantageous effectwithout disadvantageously increasing the dilutive effect.

The first vinyl-addition monomer of the formula (II) may becopolymerized with a second vinyl-addition monomer of the formula (II)wherein R₁ is H or CH₃, A is O or NH, B is an alkylene or branchedalkylene or oxyalkylene group having from 1 to 5 carbons, X is acounterion, and R₂, R₃ or R₄ is selected from the group consisting ofC₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅. In this case, the amount of thefirst monomer is preferably greater than the amount of the secondmonomer on a molar basis. Also, if R₂, R₃ and R₄ in the first monomer ofthe formula (II) together contain a total of 3 carbon atoms, then themonomers are preferably free of hydrophobic monomers.

Likewise, if the first polymer contained in an aqueous dispersion of theinstant invention is comprised of a first recurring unit of the formula(I) as set forth above, and is further comprised of a second recurringunit of formula (I) wherein R₁ is H or CH₃, A is O or NH, B is analkylene or branched alkylene or oxyalkylene group having from 1 to 5carbons, X is a counterion, and R₂, R₃ or R₄ is selected from the groupconsisting of C₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅, then the amount of thefirst recurring unit is preferably greater than the amount of the secondrecurring unit on a molar basis. Also, if R₂, R₃ and R₄ in the firstrecurring unit of the formula (I) together contain a total of 3 carbonatoms, then the first polymer is preferably devoid of hydrophobicrecurring units.

The amount of the first cationic water-soluble or water-swellablepolymer in the aqueous dispersion is as high as practicable, taking intoaccount the effect of high solids on bulk viscosity, preferably about 5%or greater, more preferably about 10% or greater, most preferably about20% or greater, by weight based on the total weight of the aqueousdispersion. Generally, the solids are not increased above an amountwhich increases the bulk viscosity to an impractical level. Practically,the amount of first cationic polymer in the aqueous dispersion is about75% or less, preferably about 60% or less, more preferably about 50% orless, by weight based on total weight. The weight average molecularweight of the first cationic polymer in the aqueous dispersion is notcritical and depends on the application, but is generally higher thanabout 1,000,000, preferably greater than about 2,000,000, morepreferably greater than about 5,000,000, and most preferably greaterthan about 10,000,000. Molecular weights of polymers are weight averageand may be determined by means known to those skilled in the art,preferably by light scattering.

The aqueous dispersions of the instant invention are generally comprisedof a discontinuous phase of small aqueous droplets, containing polymerthat is comprised predominately of the first cationic water-soluble orwater-swellable polymer, that are dispersed in the aqueous continuousphase, although of course minor amounts of said first polymer may befound in the continuous phase. Thus, the first cationic water-soluble orwater-swellable polymer generally constitutes more than 50%, preferablymore than 75%, of the polymer in a typical small aqueous droplet. Theamount of first cationic polymer in the discontinuous and continuousphases may be determined by known analytical techniques e.g. Ramanmicroscopy. Although large aqueous droplets or gel particles may beformed by adding dry or gel polymer to the other components as in U.S.Pat. No. 4,673,704 and EP 0 170 394 A2, the aqueous dispersions of theinstant invention are preferred because it is generally more desirablefor the first cationic polymer to be in the form of small droplets whichare generally held suspended in a continuous matrix of the aqueous phaseand do not generally rest substantially in contact with one another.Although aqueous dispersions prepared by polymerization of monomers asherein described may sometimes have an average droplet size of about 30microns or more, the average droplet size is generally less than about30 microns, preferably less than 20 microns, more preferably about 15microns or less. Droplet size of a non-spherical droplet is the lengthalong a major axis. Droplet size and shape tend to be a function ofreactor conditions such as stirring rate, reactor configuration, type ofstirrer, etc. Preferably, the size of the droplets is chosen by carryingout the polymerization in the presence of one or more insolublepolymeric seeds, said polymeric seeds being insoluble in an aqueoussolution having the same inorganic salt concentration as said aqueousdispersion.

The aqueous dispersions of the instant invention contain a secondwater-soluble polymer, preferably a vinyl-addition polymer, that isdifferent from and, preferably, incompatible with, said firstwater-soluble or water-swellable cationic polymer. The second polymer isdifferent from the first polymer when it can be distinguished from thefirst polymer on the basis of a particular physical characteristic e.g.chemical composition, charge, molecular weight, molecular weightdistribution, distribution of recurring units along the polymer chain,etc., by known characterization methods e.g. spectroscopy,chromatography, etc. The second polymer is incompatible with the firstpolymer when solutions of the two polymers, at the concentrationspresent in the aqueous dispersion, do not form a homogenous mixture whenblended, or do not form a homogenous mixture when one polymer is formedby polymerization of monomers in the presence of the other polymer.

The second, preferably cationic, water-soluble polymer in the aqueousdispersion of the instant invention is generally dissolved in theaqueous continuous phase, although of course minor amounts may be foundin the discontinuous phase. The amount of second polymer in thediscontinuous and continuous phases may be determined by knownanalytical techniques e.g. Raman microscopy. The second polymer may beany nonionic water-soluble polymer, preferably a polyalkyleneoxide, apolyvinylalcohol, polyvinylpyridine, polyvinylpyrollidone,polyhydroxylalkyl(alk)acrylate, etc., most preferablypoly(meth)acrylamide. Even more preferably, the second water-solublepolymer is cationic. The second polymer may be any cationic polymer, andthe charge may vary over a broad range by containing about 1% to about100% cationic recurring units, preferably about 10% or greater, morepreferably about 20% or greater, even more preferably about 30% orgreater, by mole based on total moles of recurring units in the polymer.Although in some cases the second cationic polymer may contain about 70%or less, or even about 50% or less, of cationic recurring units,preferably the second polymer is predominately cationic i.e. containsmore than 50% cationic recurring units, by mole based on total moles ofrecurring units in the polymer; most preferably about 80% or greater ofrecurring cationic units, same basis. Cationic recurring units may beformed by polymerization of cationic monomers or by post-reaction ofpolymer as above, and may be a copolymer and may contain other cationicrecurring units or nonionic recurring units as above. Preferred secondcationic water-soluble polymers contain recurring units ofdiallyldialkylammonium halide, methyl chloride quaternary salt ofdialkylaminoalkyl(alk)acrylate, dimethyl sulfate quaternary salt ofdialkylaminoalkyl(alk)acrylate, methyl chloride quaternary salt ofdialkylaminoalkyl(alk)acrylamide, or dimethyl sulfate quaternary salt ofdialkylaminoalkyl(alk)acrylamide. Especially preferred second cationicwater-soluble polymers contain recurring units ofdiallyldimethylammonium chloride, methyl chloride quaternary salt ofdimethylaminoethyl(meth)acrylate, or dimethyl sulfate quaternary salt ofdimethylaminoethyl(meth)acrylate. One or more second cationic polymersmay be used. Other cationic polymers and copolymers such as polyaminesand condensation polymers made from monomers such as epichlorohydrin anddimethylamine are also useful in the practice of this invention.Polyamines are generally well-known and include reaction products ofmono-, di- and/or triamines with epihalohydrin and/or di- ortrihaloalkane, where the ratio of the various constituents may bemanipulated to give a polyamine product having the desired molecularweight.

Depending on the application, it may be preferable for the secondpolymer to be cationic in order to maximize the cationic charge densityof the aqueous dispersion. Also, for embodiments which contain salt, itmay be preferable for the second polymer to be cationic because cationicpolymers are often more soluble in salt solution than nonionic polymers.

The amount of the second, preferably cationic, water-soluble polymer inthe aqueous dispersion is generally chosen to control aqueous dispersionproperties e.g. performance, bulk viscosity, charge, molecular weight,solubility rate, physical stability, e.g. settling, etc. Generally, theamount of said second polymer is about 5% or greater, preferably about10% or greater, more preferably about 20% or greater, most preferablyabout 30% or greater, by weight based on the amount of first cationicwater-soluble polymer. Practically, the amount of second water-solublepolymer in the aqueous dispersion is 100% or less, preferably about 80%or less, more preferably about 50% or less, by weight based on theamount of first cationic water-soluble polymer. In certain preferredembodiments, the amounts of the first and second polymers are effectiveto form an aqueous dispersion. In some embodiments, an aqueousdispersion is not formed in the absence of the second polymer, and ahomogeneous composition is obtained instead. Practically, the amount offirst and second polymer may be found by routine experimentation, anddifferent amounts will ordinarily be used depending on the identity ofthe first and second polymers, the total polymer solids level, the bulkviscosity, cost, ease of production, product performance, etc.

The weight average molecular weight of the second water-soluble polymerin the aqueous dispersion is also generally chosen to provide the mostadvantageous effect, e.g. bulk viscosity, performance, cost, etc., butis generally higher than about 10,000, preferably greater than about50,000, more preferably greater than about 500,000, and most preferablygreater than about 1,000,000. Molecular weights of polymers are weightaverage and may be determined by means known to those skilled in theart, preferably by light scattering. The second water-soluble polymer isprimarily in the continuous phase of the aqueous dispersion, although ofcourse minor amounts may be contained in the dispersed droplets.Preferably, the aqueous dispersions of the instant invention areheterogeneous compositions in which more than 50%, preferably about 75%or more, of the first cationic water-soluble or water-swellable polymeris in the form of a discontinuous phase of aqueous droplets that aredispersed in an aqueous solution that is comprised of more than 50%,preferably about 75% or more, of the second, preferably cationic,water-soluble polymer.

The aqueous dispersions of the instant invention may contain a thirdwater-soluble or water-swellable polymer that is different from thefirst or second polymers. For instance, the third polymer may also becontained in droplets dispersed in the aqueous solution, in which caseit may be described as discussed above for the first cationic polymer.The third polymer may also be dissolved in the aqueous solution alongwith the second polymer, in which case it may be described as discussedabove for the second polymer. Preferably, the third polymer is cationic.

A third aqueous dispersion, containing three or more polymers, may beformed by blending first and second aqueous dispersions of the instantinvention, wherein the first and second aqueous dispersions aredifferent from each other. Blending is generally carried out byintermixing the aqueous dispersions, typically with stirring. Blendingmay be advantageous to achieve a balance of properties exhibited by theindividual aqueous dispersions, e.g. performance, charge, total polymersolids, cost, molecular weight, etc. Surprisingly, in many cases theblends are stable, e.g. remain in the form of aqueous dispersions havinglow bulk viscosity e.g. less than 10,000 centipoise for periods of oneweek or more, even when the salt or second polymer level in the blend isgreatly different from the level needed to obtain a stable product forone or both of the dispersed polymers, if formulated alone. Alsosurprisingly, the bulk viscosity of the blend is often lower than thebulk viscosity of any of the individual aqueous dispersions.

The molecular weight of the aqueous dispersion, as that term is usedherein, is simply the weight average molecular weight of the polymerscontained therein, obtained by subjecting the entire dispersion to asuitable molecular weight characterization technique e.g. lightscattering. Since the aqueous dispersion contains two or more differentpolymers, each of which may have a molecular weight and molecular weightdistribution different from the other(s), the molecular weightdistribution of the aqueous dispersion may be multimodal. The molecularweight of the aqueous dispersion is generally about 1,000,000 orgreater, preferably greater than 2,000,000, more preferably about3,000,000 or greater, most preferably about 5,000,000 or greater.

In some cases it may be more convenient to characterize the aqueousdispersion in terms of standard viscosity instead of by molecularweight. As used herein, “standard viscosity” is determined by: dilutingan aqueous dispersion with water to form an aqueous admixture (in thecase of water-swellable polymers) or solution (in the case ofwater-soluble polymers) having a polymer concentration of about 0.2%;mixing together 8.0 g of this aqueous admixture or solution with 8.6 gof 2M NaCl; and then measuring the viscosity of the resultant mixture at25° C. on a rotating cylinder viscometer e.g. Brookfield Viscometerequipped with a UL adapter at 60 rpm. The standard viscosities of theaqueous dispersions of the instant invention are generally about 1.5centipoise or greater, preferably about 1.8 centipoise or greater, morepreferably about 2.0 centipoise or greater, most preferably about 2.5centipoise or greater, depending on the application.

The aqueous dispersions of the instant invention may also be intermixedwith water-in-oil emulsions or microemulsions of water-soluble polymersto form compositions which, though they contain oil, containproportionately less oil than the water-in-oil emulsions ormicroemulsions from which they are derived. Consequently, thesecompositions may advantageously produce less secondary pollution, havelower flammability, etc.

Certain embodiments of the instant invention require salt. Effectiveamounts of salt tend to reduce the bulk viscosity of the aqueousdispersion. The salt may be any inorganic salt, preferably a kosmotropicsalt e.g. a chloride, sulfate, phosphate, or hydrogenphosphate salt,more preferably ammonium sulfate, sodium chloride, and sodium sulfate,most preferably sodium sulfate and ammonium sulfate. The counterion maybe any counterion, e.g. Group IA and Group IIA metal ions, ammonium,etc., preferably ammonium, sodium, potassium and magnesium. Mixtures ofsalts may be used, and the amount of salt may be chosen to achieve adesirable bulk viscosity or any other desirable effect. Since the saltmay have a dilutive effect, in certain preferred embodiments the salt isonly added in amounts so as to achieve a homogeneous composition in theabsence of the second water-soluble polymer. In these embodiments, theaqueous dispersion is not formed by the action of the salt, but by theinteraction of the first and second polymers. Effective orviscosity-reducing amounts of salt may be found through routineexperimentation and are generally chosen to reduce the bulk viscositywithout causing precipitation of the polymer. In other preferredembodiments, the salt is only added in amounts so as to achieve ahomogeneous composition in the absence of the first cationic polymer. Inembodiments where salt is helpful but not necessary, salt levels mayrange upwards from 0%, preferably about 3% or greater, most preferablyabout 5% or greater, by weight based on total weight, depending on theupper limit to solubility, because solubility of the salt in the aqueousdispersion is preferred. In embodiments where salt is necessary, saltlevels are chosen to favorably influence product attributes such ascost, bulk viscosity, etc. and may range upwards from about 1%,preferably about 3% or greater, most preferably about 5% or greater, byweight based on total weight, depending on the upper limit tosolubility, because solubility of the salt in the aqueous dispersion ispreferred. Frequently, no practical effect of the salt is observed aboveabout 30%, so salt levels are generally about 30% or less, preferablyabout 25% or less, by weight based on total weight. Practically, thesalt level may be determined by routine experimentation, e.g. balancingthe tendency for positive product attributes e.g. lower bulk viscositiesresulting from higher salt levels, against the negative aspects of saltuse e.g. cost and dilutive effect.

Surprisingly, it has been discovered that mixtures of chaotropic saltswith kosmotropic salts, or anionic organic salts with kosmotropic salts,have a tendency to reduce the bulk viscosity of the aqueous dispersion.In many cases, the salt mixture is more effective than either saltalone, on a weight basis. Useful chaotropic salts include thiocyanates,perchlorates, chlorates, nitrates, bromides, iodides, and mixturesthereof, preferably sodium thiocyanate and sodium iodide. Useful anionicorganic salts include anionic surfactants and anionic hydrotropic salts,preferably aryl and substituted aryl sulfonates having from 6 to 22carbons, preferably 6 to 18 carbons, and alkyl and substituted alkylsulfonates having from 2 to 22 carbons, preferably 4 to 18 carbons, andmixtures thereof. Especially preferred anionic organic salts aredialkylsulfosuccinates, diarylsulfosuccinates, benzenesulfonates,benzenedisulfonates, naphthalensulfonates, naphthalenedisulfonates, andmixtures thereof; 1,3-benzendisulfonates are most preferred. Counterionsto the chaotropic and anionic organic salts may be any typicalcounterion, e.g. Group IA metal ions, ammonium, etc., preferablyammonium, sodium, and potassium. Effective or viscosity-reducing amountsof chaotropic and anionic organic salts may be found through routineexperimentation and are generally chosen to reduce the bulk viscositywithout causing precipitation of the polymer. In certain preferredembodiments, the amounts of chaotropic salt, or anionic organic salt,and kosmotropic salt are chosen such that a homogeneous composition isobtained in the absence of the second cationic polymer; i.e. theconcentration of the salts is such that the first cationic polymer isnot precipitated in the absence of the second cationic polymer.Generally, amounts of chaotropic, or anionic organic, salts are about10% or less, preferably about 5% or less, and generally 0.5% or more,preferably 1% or more, by weight based on total weight. At very lowchaotropic or anionic organic salt levels, the viscosity-reducing effectof the salt is negligible, whereas the salt may cause undesirableprecipitation or layering at high levels of incorporation. To achieve acertain bulk viscosity, amounts of kosmotropic salts used with thechaotropic, or anionic organic salt, are generally less than when thekosmotropic salt is used alone, but still within the ranges given abovefor the use of inorganic or kosmotropic salts alone.

The aqueous dispersions of the instant invention generally have lowerbulk viscosities than comparable aqueous dispersions. A comparableaqueous dispersion is generally one which is substantially identical inmany functional aspects, but lacks a particular element of the instantinvention. In general, the aqueous dispersions of the instant inventionhave lower bulk viscosities than comparable aqueous dispersions whichhave substantially the same polymer solids, cationic charge level andweight average molecular weight, but which lack an important feature ofthe instant invention e.g. lack a recurring unit of formula (I); lackthe amount of recurring units of formula I found in the aqueousdispersions of the instant invention; not made by a process whichcomprises polymerizing vinyl-addition monomers comprised of at least onemonomer of the formula (II); not made by a process which comprisespolymerizing vinyl-addition monomers comprised of the amount of monomersof the formula (II) used in the processes of the instant invention, etc.For instance, in a composition comprising an aqueous dispersioncomprised of: (a) a discontinuous phase containing polymer that iscomprised predominately of a first cationic water-soluble orwater-swellable polymer having at least one recurring unit of theformula (I), and (b) at least one second water-soluble polymer differentfrom said first polymer, a comparable aqueous dispersion may be onewhich contains the same amount of each component, except the R₂, R₃ andR₄ in the corresponding recurring formula (I) unit of the comparableaqueous dispersion together contain a total of 3 carbon atoms, insteadof the 4 or more carbons in the corresponding recurring unit of formula(I) in the claimed aqueous dispersion.

Surprisingly, aqueous dispersions having formula (I) recurring units inwhich R₂, R₃ and R₄ contain four or, preferably, five carbons generallyhave bulk viscosities which are dramatically lower than the bulkviscosities of aqueous dispersions that are substantially identicalexcept that R₂, R₃ and R₄ contain only three carbons. The bulk viscosityof aqueous dispersions is typically influenced by e.g. total polymersolids, salt level, polymer type, ratio of first cationic polymer tosecond cationic polymer, etc. as disclosed herein. Although aqueousdispersions having bulk viscosities of about 20,000 centipoise (cps) ormore, or even about 200,000 cps or more may be suitable in certaincircumstances, much lower bulk viscosities are generally preferred forease of handling. Aqueous dispersions having bulk viscosities of about20,000 centipoise (cps) or less, preferably about 10,000 cps or less,more preferably about 8,000 cps or less, even more preferably about5,000 cps or less, most preferably about 2,500 cps or less, may beobtained by the practice of the instant invention. Bulk viscosity may bemeasured by any convenient method known to those skilled in the art,preferably a rotating cylinder viscometer as described in the Examplesbelow.

Aqueous dispersions are preferred which have as many of the followingadvantageous attributes as possible: relatively high cationic polymersolids, preferably 20% or greater, more preferably 25% or greater, byweight based on total; high molecular weight, preferably 2,000,000 orgreater, more preferably 5,000,000 or greater; reduced environmentalimpact (low VOC, substantially free of organic solvents and aromaticgroups, e.g. aromatic- or benzyl-containing oils or recurring units);minimal levels of diluents (preferably, 20% or less of salt, by weightbased on total, and polymer devoid or substantially free of hydrophobicrecurring units); bulk viscosity about 2,000 cps or less; for recurringunits based on formula (I), R₂, R₃ and R₄ together containing a total of5 carbons; and superior or equivalent performance. Products having allof these attributes may be obtained by the practice of the presentinvention.

Aqueous dispersions of water-soluble polymers are preferably formed bypolymerization of the corresponding monomers to form the first cationicwater-soluble polymer, in the presence of at least one second cationicwater-soluble polymer and, in certain embodiments, an inorganic salt.Polymerization may be effected by any initiating means, including redox,thermal or irradiating types. Examples of preferred initiators are2,2′-azobis(2-amidino-propane)dihydrochloride (V-50),2,2′-azobis(isobutyronitrile), sodium bromate/sulfur dioxide, potassiumpersulfate/sodium sulfite, and ammonium persulfate/sodium sulfite, aswell as peroxy redox initiators e.g. those disclosed in U.S. Pat. No.4,473,689. Initiator levels are chosen in a known manner so as to createpolymers of the desired molecular weight. Amounts of chain transferagents, e.g. isopropanol, lactic acid, mercaptoethanol, etc. andbranching or crosslinking agents, e.g. methylenebisacrylamide may beadded in a known manner to further adjust the properties of the firstcationic water-soluble polymer. Depending on the production conditions,e.g. types and relative amounts of chain transfer agent and branchingagent, water-swellable or branched, water-soluble polymers may beformed. In general, the use of greater amounts of branching orcrosslinking agent increases the tendency for the product to bewater-swellable instead of water-soluble, and increased amounts of chaintransfer agent tend to reduce molecular weight. When chain transferagent and branching agent are used together, water-swellable productsare more likely to be obtained at high branching agent and low chaintransfer agent levels, whereas branched, water-soluble polymers may beobtained at high chain transfer and low branching agent levels.Components may be added at any time; e.g. all of the monomers may bepresent from the onset of the polymerization, or monomers may be addedduring the course of the polymerization. If salt is used, all of thesalt may be present from the onset of the polymerization, or salt may beadded during the course of the polymerization or after polymerization iscomplete. Likewise, polymerization parameters e.g. temperature and timemay be chosen in a known manner, and may be varied during the course ofthe polymerization. Polymerization is generally effected in the presenceof an inert gas, e.g. nitrogen. Conventional processing aids e.g.chelating agents, sequestrants, pH adjusters, etc. may be added asrequired.

The aqueous dispersions of the present invention have advantageousaspects in that they are preferably substantially free of dilutivesubstances such as surfactant, oil, hydrocarbon liquids, organicsolvents, etc. Although viscosity-reducing additives e.g. glycerin,glycerol, alcohol, glycol, etc. may be present in the aqueousdispersions, amounts should be 2% or less, more preferably 1% or less,most preferably 0.1% or less, in order to maintain the advantageousproperties of the invention.

The aqueous dispersions of the instant invention may be homogenous inthe absence of a particular component e.g., said second water-solublepolymer. Homogenous compositions are generally characterized as beingclear or translucent, and are not aqueous dispersions because they donot contain dispersed droplets as described above. Depending on theembodiment, said first cationic water-soluble polymer or said secondcationic water-soluble polymer is dispersion-creating in that aqueousdispersions are not obtained in the absence of an effective ordispersion-creating amount of the particular component.

Waters used in the present invention may be from any source, e.g.process water, river water, distilled water, tap water, etc. Preferably,polymerizations are conducted in aqueous solutions that do not containsubstantial amounts of materials which detrimentally affect thepolymerization. Advantageously, the aqueous dispersions of the presentinvention tend to dissolve quickly when diluted with water.

The aqueous dispersion of the instant invention may be dehydrated toincrease the total polymer solids content, or to create substantiallydry products. Any means known in the art e.g. stripping, spray drying,solvent precipitation, etc. may be used to reduce the water content.Surprisingly, partial dehydration may reduce the bulk viscosity of anaqueous dispersion, in spite of the tendency for dehydration to increasepolymer solids. Dehydration may be performed by heating, preferablyunder reduced pressure, although of course excessive heating may bedetrimental to polymer properties. A substantially dry mass of polymermay be obtained by removal of water, and the mass may be comminuted tocreate a powdery, particulate, or granular product.

Surprisingly, substantially dry polymer products may be obtained byspray-drying the aqueous dispersions of the instant invention. Althoughoil-containing polymer emulsions and dispersions have been spray-dried,see e.g. U.S. patent application Ser. No. 08/668,288 and referencestherein, spray-drying of aqueous dispersions, which are generally freeof oil and surfactants, has not previously been reported. In accordancewith the instant invention, vinyl-addition polymer-containing aqueousdispersions may be sprayed-dried by a suitable means into a largechamber through which a hot gas is blown, thereby removing most or allof the volatiles and enabling the recovery of the dried polymer.Surprisingly, the means for spraying the aqueous dispersion into the gasstream are not particularly critical and are not limited to pressurenozzles having specified orifice sizes; in fact, any known spray-dryingapparatus may be used. For instance, means that are well known in theart such rotary atomizers, pressure nozzles, pneumatic nozzles, sonicnozzles, etc. can all be used to spray-dry the aqueous dispersion intothe gas stream. The feed rate, feed viscosity, desired particle size ofthe spray-dried product, droplet size of the aqueous dispersion, etc.are factors which are typically considered when selecting the sprayingmeans. The size and shape of the chamber, the number and type ofspraying means, and other typical operational parameters may be selectedto accommodate dryer conditions using common knowledge of those skilledin the art.

Although closed cycle spray-dryers may be used, open cycle spray-dryingsystems are preferred. Gas flow may be cocurrent, countercurrent ormixed flow, cocurrent flow being preferred. The hot gas, or inlet gas,may be any gas that does not react or form explosive mixtures with thefeed and/or spray-dried polymer. Suitable gases used as the inlet gasare gases known to those skilled in the art, including air, nitrogen,and other gases which will not cause undesirable polymer degradation orcontamination, preferably gases containing about 20% or less oxygen,more preferably about 15% or less oxygen. Most preferably, inert gasessuch as nitrogen, helium, etc. that contain about 5% or less of oxygenshould be used.

The dried polymer may be collected by various means such as a simpleoutlet, classifying cone, bag filter, etc., or the polymer may besubjected to further stages of drying, such as by fluid beds, oragglomeration. The means for collecting the dry polymer product is notcritical.

There are four interrelated operating parameters in the instantspray-drying process: gas inlet temperature, gas outlet temperature,product volatiles and residence time in the dryer. The outlettemperature generally should be about 150° C. or below, preferably about120° C. or below, more preferably less than 100° C., even morepreferably about 95° C. or below, most preferably about 90° C. or below.The outlet temperature is generally about 70° C. or higher, preferablyabout 75° C. or higher. Therefore, outlet temperatures are generallyabout 70° C. to about 150° C., preferably about 70° C. to about 120° C,more preferably about 70° C. to less than 100°, even more preferablyabout 70° C. to about 95° C., most preferably about 75° C. to about 90°C. Outlet temperatures below about 70° C. may be suitable in certaininstances, though generally this is less preferred. For instance, at thecost of efficiency, spray drying could be carried out at long residencetimes, high gas flow rates and low outlet temperatures. Generally, thedryer should be operated at the lowest possible outlet temperatureconsistent with obtaining a satisfactory product.

The inlet temperature, the feed rate, and the composition of the aqueousdispersions may all affect outlet temperatures. These parameters may bevaried to provide a desired outlet temperature. Feed rates are notcritical, and generally will vary depending on the size of the dryer andthe gas flow rate. Inlet gas temperature is less critical than outletgas temperature, and is generally about 140° C. or above, preferablyabout 160° C. or above. The inlet gas temperature is preferably about200° C. or below and more preferably about 180° C. or below. Thus,preferred inlet gas temperature ranges from about 140° C. to about 200°C., more preferably from about 160° C. to about 180° C. Proper inlet gastemperatures tend to avoid product degradation on the high side and toavoid inadequate drying on the low side.

Residence time is a nominal value obtained by dividing the volume of thedryer by the volumetric gas flow. Residence time is generally at leastabout 8 seconds, preferably at least about 10 seconds. Residence time isgenerally no more than about 120 seconds, preferably no more than about90 seconds, more preferably no more than about 60 seconds, and mostpreferably no more than about 30 seconds. Therefore, the general rangeof residence time is about 8 to about 120 seconds, preferably about 10to about 90 seconds, more preferably about 10 to about 60 seconds, andmost preferably about 10 to about 30 seconds. It is known to thoseskilled in the art that longer residence times are to be expected whenlarger dryers are used or when the dryer is run in a less efficientmanner. For instance, at the cost of efficiency, longer residence timeswould be expected at very low inlet temperatures and slow gas flowrates. As a practical matter, the residence times useful in the presentinvention may vary from the values described above, depending on thesize and type of spray dryer used, the efficiency at which it isoperated, and other operational parameters. Thus, residence timesspecified herein may be modified to accommodate dryer conditions usingcommon knowledge of those skilled in the art.

When produced according to the spray drying processes disclosed herein,polymer particles of the instant invention are generally about 10microns or greater in diameter, preferably about 40 microns or greater,more preferably about 100 microns or greater, most preferably about 200microns or greater. It is preferred that the polymer particles benon-dusting. Dusting and flow problems are typically exacerbated whenthe polymer particles are small, so larger polymer particles aregenerally desirable. However, very large particles may dissolve moreslowly. Therefore, it is generally desirable for the polymer particlesto be about 1200 microns or less in diameter, preferably about 800microns or less in diameter, more preferably about 600 microns or less,most preferably about 400 microns or less. Generally, at least about 90%of the polymer particles range in size from about 10 microns to about1200 microns, preferably at least about 95%, more preferably at leastabout 98%. The size of the polymer particles can be varied somewhat byaltering the operational parameters e.g. spray configuration, aqueousdispersion viscosity, feed rate, etc. Particles may be substantiallyspherical or non-spherical; “diameter” of a non-spherical particle isthe dimension along a major axis.

Although in some cases the polymer particles are hollow, porousstructures having at least one opening in their walls, it has beendiscovered that these features are not always necessary in order toobtain particles having desirable properties e.g. fast dissolutiontimes. In many cases, the spray-drying parameters e.g. nozzle type,nozzle size, outlet temperature, etc. needed to produce particles thatare hollow, porous structures having at least one opening in their wallsare inconvenient or uneconomical, and it is advantageous to produceparticles that lack some or all of these features.

The particles formed by the spray-drying processes of the instantinvention may be screened to remove an oversize or undersize fraction.Oversize particles may be fragmented by e.g. grinding, whereasundersized particles are generally agglomerated. Sizes may be determinedby methods known to those skilled in the art e.g. sieving, screening,light scattering, microscopy, microscopic automated image analysis, etc.

Surprisingly, the bulk densities of the spray-dried polymer particles ofthe instant invention are generally greater than the bulk densities ofdry polymers prepared by precipitation of e.g. water-in-oil emulsions ofthe same polymer. Polymer particles having greater density may beadvantageous because they occupy a smaller volume, resulting in e.g.lower shipping and storage costs. Whereas the densities of precipitatedpolymers are usually less than about 0.35 grams per cubic centimeter(g/cc), the bulk densities of the spray-dried polymer particles of theinstant invention are generally about 0.35 g/cc or greater, preferablyabout 0.4 g/cc or greater, more preferably about 0.45 g/cc or greater,most preferably about 0.50 g/cc or greater. The bulk densities of thespray-dried polymer particles of the instant invention are generallyabout 1.1 g/cc or less, preferably about 1.0 g/cc or less, morepreferably about 0.95 g/cc or less, most preferably about 0.90 g/cc orless. Therefore, the bulk densities of the spray-dried polymer particlesof the instant invention generally range from about 0.35 to about 1.1g/cc, preferably about 0.4 to about 1.0 g/cc, more preferably about 0.45to about 0.95 g/Cc, most preferably about 0.50 to about 0.90 g/cc.

Under the conditions of drying set forth herein, the polymer particlesproduced by the processes described herein are substantially dry. Asused to describe the polymer produced herein, “substantially dry”generally means that the polymer contains about 12% or less volatiles,preferably about 10% or less by weight, based on the weight of the spraydried polymer. The polymer generally contains about 2% or morevolatiles, preferably about 5% or more, by weight based on total weight,and most preferably contains from about 8% to about 10% volatiles byweight, same basis. The volatiles are measured by determining the weightloss on drying the polymer product at about 105° C. for about 30minutes.

It has also been discovered that agglomeration of the polymer particlesof the instant invention may improve the flow properties and dissolutiontimes of the polymers. Agglomeration is a known process for increasingparticle size and various methods for agglomerating particles are knownto those skilled in the art, e.g. “Successfully Use Agglomeration forSize Enlargement,” by Wolfgang Pietsch, Chemical Engineering Progress,April 1996, pp. 29-45; “Speeding up Continuous Mixing Agglomeration withFast Agitation and Short Residence Times,” by Peter Koenig, Powder andBulk Engineering, February 1996, pp. 67-84. Known agglomeration methodssuch as natural agglomeration, mechanical agglomeration, tumble orgrowth agglomeration, pressure agglomeration, binderless agglomeration,agglomeration with binders, etc. may be used to agglomerate the polymerparticles of the instant invention. Agglomeration may optionally befollowed by drying e.g. fluid bed drying, to remove binder e.g. water.Pressure agglomeration is preferred, and mechanical agglomeration usinga water binder, followed by fluid bed drying is most preferred.

The agglomerates formed by agglomerating the polymer particles of theinstant invention tend to have improved flow properties and fasterdissolution times when compared to the unagglomerated polymer particles.Preferably, the agglomerates are non-dusting. Typically, about 90% ofthe agglomerates of the instant invention have an agglomerate size ofabout 120 microns or greater, preferably about 160 microns or greater,more preferably about 200 microns or greater, most preferably about 300microns or greater. Generally, about 90% of the agglomerates have anagglomerate size of about 1500 microns or less, preferably about 1200microns or less, more preferably about 1100 microns or less, mostpreferably about 1000 microns or less. Thus, about 90%, preferably 95%,of the agglomerates have a size in the range of about 120 to about 1500microns, preferably about 160 microns to about 1200 microns, morepreferably about 200 microns to about 1100 microns, most preferablyabout 300 microns to about 1000 microns Usually, at least about 5% ofthe agglomerates, preferably at least about 10%, most preferably atleast about 15%, are larger than about 900 microns. The agglomeratesformed by agglomerating the spray-dried particles of the instantinvention may be screened to remove an oversize or undersize fraction.Preferably, agglomerates larger than about 1200 microns and smaller thanabout 175 microns are removed by e.g. screening. Oversize agglomeratesare generally fragmented by e.g. grinding, whereas undersizedagglomerates are generally recycled into the agglomerator.

The bulk density values of the agglomerates of the instant inventiontend to be lower than the bulk density values of the spray-driedparticles from which they are formed. The bulk densities of theagglomerates of the instant invention are generally about 0.35 g/cc orgreater, preferably about 0.4 g/cc or greater, more preferably about0.45 g/cc or greater, most preferably about 0.50 g/cc or greater. Thebulk densities of the agglomerates of the instant invention aregenerally about 1.0 g/cc or less, preferably about 0.95 g/cc or less,more preferably about 0.90 g/cc or less, most preferably about 0.85 g/ccor less. Therefore, the bulk densities of the agglomerates of theinstant invention generally range from about 0.35 to about 1.0 g/cc,preferably about 0.4 to about 0.95 g/cc, more preferably about 0.45 toabout 0.90 g/cc, most preferably about 0.50 to about 0.85 g/cc.

In order to obtain agglomerates of a preferred size, it is preferredthat the polymer particles themselves be of such a size that they areagglomerable. Agglomeration obviously tends to multiply the averageparticle size, so that it is frequently easier to cause large increasesin particle size than it is to cause small increases in particle size.Therefore, to produce agglomerates of a preferred size or size range, itis generally preferred to agglomerate particles that are much smallerthan the desired agglomerate size, rather than particles that are onlyslightly smaller. Agglomerable particles are generally those that may beconveniently agglomerated to produce agglomerates having a preferredsize. It is possible, but less preferred, to agglomerate largerparticles to produce agglomerates that are larger than desired, thenremove the oversize agglomerates as described above.

The substantially dry polymer particles and agglomerates of the presentinvention are generally comprised of the polymer that was contained inthe aqueous dispersion that was spray-dried, as discussed hereinabove.

Spray-drying of the aqueous dispersions of the instant invention isadvantageous because typically 90% or greater, preferably 95% orgreater, most preferably substantially all, of the resultant spray-driedpolymer particles each individually contains two or more water-solubleor water-swellable vinyl-addition polymers, so that stratificationeffects may be minimized. Stratification may occur when two differentdry polymers having differing particle sizes or particle sizedistributions are blended together because of the tendency for thelarger particles to settle towards the bottom of the container.Stratification on storage may affect blend product performance as thetop of the container tends to become enriched in the polymer having thesmaller particle size. For obvious reasons, changes in productperformance as a function of storage depth are to be avoided, and it isgenerally preferred that each polymer in a blend be of similar particlesize, see e.g. EP 479 616 A1 and U.S. Pat. No. 5,213,693. A dry blend ofthe two different polymers is likely to exhibit greater stratificationthan a dry blend obtained by spray-drying the instant aqueousdispersions because the majority of the spray-dried polymer particles ofthe instant invention each individually contains two or morewater-soluble or water-swellable vinyl-addition polymers. Surprisingly,the spray-dried aqueous dispersions of the instant invention tend todissolve faster than polymers obtained by spray-drying conventionalwater-in-oil emulsions of similar polymers.

A suspension of dispersed solids may be dewatered by a method whichcomprises (a) intermixing an effective amount of an aqueous dispersionof polymers, or aqueous admixture thereof, with a suspension ofdispersed solids, and (b) dewatering said suspension of dispersedsolids. Substantially dry polymers derived from the aqueous dispersionsof the instant invention as described above may also be used to dewatersuspended solids. For instance, a suspension of dispersed solids may bedewatered by a method which comprises (a) intermixing an effectiveamount of a substantially dry water-soluble or water-swellable polymer,or aqueous admixture thereof, with a suspension of dispersed solids, and(b) dewatering said suspension of dispersed solids. Preferably, anaqueous admixture of the dry polymer or aqueous dispersion is preparedby intermixing the dry polymer or aqueous dispersion with water, morepreferably by dissolving the dry polymer or aqueous dispersion in waterto form a dilute polymer solution. Effective amounts of dry polymer oraqueous dispersion are determined by methods known in the art,preferably by routine laboratory or process experimentation.

Examples of suspensions of dispersed solids which may be dewatered bymeans of the instant invention are municipal and industrial wastedewatering, clarification and settling of primary and secondaryindustrial and municipal waste, potable water clarification, etc.Because of the advantageous aspects of the invention e.g. substantiallyoil-free, minimum amounts of inactive diluents, little or no surfactant,etc., the polymers may be especially well-suited to situations wherepart or all of the dewatered solids or clarified water is returned tothe environment, such as sludge composting, land application of sludge,pelletization for fertilizer application, release or recycling ofclarified water, papermaking, etc. Other applications which may benefitfrom the advantageous aspects of the instant inventions include soilamendment, reforestation, erosion control, seed protection/growth, etc.,where the aqueous dispersion or dry polymer, preferably an aqueousadmixture thereof, is advantageously applied to soil.

Other examples of suspensions of dispersed solids which may be dewateredby means of the instant invention are found in the papermaking area,e.g. the aqueous dispersions or dry polymer may be used as retentionaids, drainage aids, formation aids, washer/thickener/drainageproduction aid (DNT deink application), charge control agents,thickeners, or for clarification, deinking, deinking process waterclarification, settling, color removal, or sludge dewatering. Thepolymers of the instant invention may also be used in oil fieldapplications such as petroleum refining, waster clarification, wastedewatering and oil removal.

Dewatering and clarification applications for the aqueous dispersionsand dry polymers of the instant invention may also be found in the foodprocessing area, including waste dewatering, preferably waste dewateringof poultry beef, pork and potato, as well as sugar decoloring, sugarprocessing clarification, and sugar beet clarification.

Mining and mineral applications for the aqueous dispersions and drypolymers of the instant invention include coal refuse dewatering andthickening, tailings thickening, and Bayer process applications such asred mud settling, red mud washing, Bayer process filtration, hydrateflocculation, and precipitation.

Biotechnological applications for the aqueous dispersions and drypolymers of the instant invention include dewatering and clarificationof wastes and preferably, dewatering and clarification of fermentationbroths.

The aqueous dispersions of the instant invention may be employed in theabove applications alone, in conjunction with, or serially with, otherknown treatments.

All patents, patent applications, and publications mentioned above arehereby incorporated herein by reference. Unless otherwise specified, allpercentages mentioned herein are understood to be on a weight basis.

The Standard Viscosity (SV) values in the following Examples weredetermined by mixing together 8.0 g of a 0.2 wt. % polymer solution inwater and 8.6 g of 2M NaCl, then measuring the viscosity of theresultant solution at 25° C. on a Brookfield Viscometer equipped with aUL adapter at 60 rpm. Molecular weights were determined by highperformance size exclusion chromatography using a light scatteringdetector.

The bulk density of polymer particles and agglomerates was determined byadding the particles or agglomerates to a suitable preweighed measuringcontainer and “tapping” or slightly agitating the container to cause theparticles or agglomerates to settle. The volume of the polymer was thenread from the measuring container, the measuring container weighed, andthe bulk density calculated in units of grams per cubic centimeter(g/cc).

EXAMPLE 1

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and a nitrogen inlet tube was charged with 17.10 parts deionized waterand 9 parts of a 40% aqueous solution of the polymer obtained bypolymerizing the methyl chloride quaternary salt ofdimethylaminoethylmethacrylate (poly(DMAEM.MeCl)), weight averagemolecular weight about 200,000. After completion of dissolution, 7.08parts of a 53.64% aqueous solution of acrylamide (AMD), and 14.56 partsof a 72.80% solution of the dimethyl sulfate salt ofdiethylaminoethylacrylate (DEAEA.DMS) were added and mixed. To thismixture, 8.1 parts ammonium sulfate, 0.7 parts citric acid, and 2.02parts of a 1% solution of chelant ethylenediaminetetraacetic acidtetrasodium salt (EDTA) were added and mixed. The pH of the mixture wasabout 3.3. The vessel was sealed and sparged with nitrogen for 30minutes, and then polymerization was started by adding 1.44 parts of 1%aqueous solution of 2,2′-azobis(2-amidino-propane)dihydrochloride(V-50). The reaction mixture was heated to 40° C. for 2 hours and thenraised to 50° C. and held for an additional 8 hours. The conversion wasgreater than 99%. A stable fluid aqueous dispersion was obtained. Thebulk viscosity (BV) of the dispersion was 2250 centipoise (cps) showingpreferable fluidity as measured with a Brookfield Viscometer, No. 4spindle, 30 rpm at 25° C. The dispersion was dissolved to give astandard viscosity (SV) of 2.56 cps.

EXAMPLES 2-8

Additional aqueous dispersions were prepared in the same manner asExample 1, showing the effect of various polymer and ammonium sulfatesalt levels on bulk viscosity as shown in Table 1.

TABLE 1 Ex- am- FIRST SECOND ple % TOTAL POLYMER POLYMER % BV SV No.SOLIDS % SOLIDS % SOLIDS SALT (cps) (cps) 1 30 24 6 13.5 2,250 2.56 2 3024 6 12.5 6,600 2.2 3 30 24 6 13 6,000 2.37 4 30 24 6 13.5 2,960 2.3 530 24 6 13.5 2,300 2.35 6 30 25 5 13.5 2,640 2.61 7 30 24 6 14 3,4702.39 8 30 24 6 15 7,080 2.17

EXAMPLE 9

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and a nitrogen inlet was charged with 72.60 parts ofdeionized water and 30.8 parts of a 40% aqueous solution ofpoly(DMAEM.MeCl), weight average molecular weight about 222,600. Afterdissolution was complete, 24.37 parts of a 53.33% aqueous solution ofacrylamide and 45.93 parts of a 79% aqueous solution of DEAEA.DMS wereadded and mixed. To this mixture, 31.9 parts ammonium sulfate, 2.57parts citric acid, and 6.9 parts of 1% solution of EDTA were added andmixed. The pH of the mixture was about 3.3. The vessel was sealed andsparged with nitrogen for 30 minutes, and then polymerization wasstarted by adding 4.93 parts of 1% solution of V-50. The reactionmixture was heated to 40° C. for 2 hours and then raised to and held at50° C. for 4 hours. The overall conversion was greater than 99%. Astable fluid aqueous dispersion was obtained. The bulk viscosity of thisdispersion was about 1460 cps showing preferable fluidity as measuredwith a Brookfield Viscometer, No. 4 spindle, 30 rpm at 25° C. Thedispersion was dissolved to give a SV of 2.40 cps.

EXAMPLES 10-33

Additional aqueous dispersions were prepared in the same manner asExample 9 demonstrating the effect of total polymer solids, ratio offirst cationic to second cationic polymer, second cationic polymermolecular weight, and ammonium sulfate salt level on the bulk viscosity(BV) of the aqueous dispersion, as shown in Table 2.

TABLE 2 FIRST SECOND SECOND EXAMPLE % TOTAL POLYMER POLYMER POLYMER %NO. SOLIDS % SOLIDS % SOLIDS MW SALT BV (cps) SV (cps) 9 28 22.4 5.6222,600 14.5 1,460 2.40 10 28 22.4 5.6 194,000 14.5 2,250 2.52 11 2822.4 5.6 199,300 14.5 1,440 2.52 12 28 22.4 5.6 172,870 14.5 2,940 2.6113 28 22.4 5.6 221,500 14.5 1,970 2.52 14 28 22.4 5.6 159,000 14.5 2,7402.59 15 28 22.4 5.6 145,000 14.5 2,920 2.65 16 28 22.4 5.6 199,300 14.52,150 2.86 17 30 24 6 242,900 13.5 2,620 2.49 18 30 24 6 230,600 13.53,710 2.4 19 30 24 6 230,600 14 2,200 2.39 20 30 24 6 230,600 14.5 1,8002.54 21 30 24 6 230,600 15 3,260 2.49 22 28 22.4 5.6 230,600 15   9822.49 23 28 22.4 5.6 230,600 15.5   900 2.45 24 28 23.5 4.5 230,600 15.51,380 2.77 25 27 22.66 4.34 230,600 15.5 1,600 2.61 26 27 22.66 4.34230,600 16 1.770 2.82 27 30 24 6 230,600 14.5 1,770 2.43 28 28 22.4 5.6230,600 15.5 1,820 2.56 29 28 22.4 5.6 230,600 16 3,120 2.44 30 28 23 5230,600 15 1,620 2.5 31 28 23 5 230,600 15.5   962 2.67 32 28 23 5230,600 16 1,500 2.59 33 28 22.4 5.6 230,600 15.5 1,260 2.51

EXAMPLE 34

This polymerization was carried out in the same manner as Example 9,except that a poly(DMAEM.MeCl) having a weight average molecular weightof about 395,000 was used. A stable fluid aqueous dispersion wasobtained. The bulk viscosity of this aqueous dispersion was about 5100cps showing preferable fluidity as measured with a BrookfieldViscometer, No. 4 spindle, 30 rpm at 25° C. The dispersion was dissolvedto give a SV of 2.35 cps.

EXAMPLE 35

This polymerization was carried out in the same manner as Example 34,except that 2.46 parts of 10% glycerol solution was added.Polymerization proceeded smoothly. A stable fluid aqueous dispersion wasobtained. The bulk viscosity of this dispersion was about 3700 cps asmeasured with a Brookfield Viscometer, No. 4 spindle, 30 rpm at 25° C.showing improved fluidity. The bulk viscosity was greatly reducedrelative to Example 34, demonstrating the viscosity-reducing effect ofthe glycerol additive. The dispersion was dissolved to give a SV of 2.35cps.

EXAMPLE 36

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 39.73 partsdeionized water and 30.1 parts of 41% poly(DMAEM.MeCl), weight averagemolecular weight about 395,000. After completion of dissolution, 23.77parts of a 53.57% aqueous solution of acrylamide, 45.20 parts of an 80%aqueous solution of DEAEA.DMS and 38.7 parts of 1% aqueous solution oftertiary butyl acrylamide were added and mixed. To this mixture, 49.28parts ammonium sulfate, 2.57 parts citric acid, and 3.45 parts of 2%EDTA were added and mixed. The pH of the mixture was about 3.3. Thevessel was sealed and sparged with nitrogen for 30 minutes, and thenpolymerization was started by adding 2.46 parts of 2% V-50. The reactionmixture was raised to 40° C. for 2 hours and then raised to 50° C. foran additional 4 hours. The overall conversion was greater than 99%. Astable fluid aqueous dispersion was obtained. The bulk viscosity of thisaqueous dispersion was about 1900 cps as measured with a BrookfieldViscometer No. 4 spindle, 30 rpm at 25° C., showing improved fluiditycompared to Example 34 and demonstrating the effect of incorporatinghydrophobic recurring units of tertiary butyl acrylamide. The aqueousdispersion was dissolved to give a SV of 2.32 cps.

EXAMPLE 37

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 78.84 partsdeionized water and 30.1 parts of 41% poly(DMAEM.MeCl), weight averagemolecular weight about 395,000. After completion of dissolution, 20.95parts of a 53.57% aqueous solution of acrylamide, 42.73 parts of a 80%aqueous solution of DEAEA.DMS and 4.84 parts of a 80% aqueous solutionof the benzyl chloride quaternary salt of dimethylaminoethyl acrylate(DMAEA.BzCl) were added and mixed. To this mixture, 49.28 parts ammoniumsulfate, 2.57 parts citric acid, and 3.45 parts of 2% EDTA were addedand mixed. The pH of the mixture was about 3.3. The vessel was sealedand sparged with nitrogen for 30 minutes, and then polymerization wasstarted by adding 2.46 parts of 2% V-50. The reaction mixture was raisedto 40° C. for 2 hours, and then raised to and held at 50° C. for 4hours. The overall conversion was greater than 99%. A stable fluidaqueous dispersion was obtained. The bulk viscosity of this dispersionwas about 3840 cps as measured with a Brookfield Viscometer No. 4spindle, 30 rpm at 25° C. showing preferable fluidity. The dispersionwas dissolved to give a SV of 2.14 cps.

EXAMPLE 38

A suitable vessel with an external jacket for heating or cooling wasequipped with a mechanical stirrer, reflux condenser, thermocouple andnitrogen inlet tube. The vessel was charged with 294.47 parts deionizedwater and 117.60 parts of 40% aqueous solution of poly(DMAEM.MeCl),weight average molecular weight about 210,000. After completion ofdissolution, 94.03 parts of a 52.77% aqueous solution of acrylamide and173.18 parts of an 80% aqueous solution of DEAEA.DMS were added andmixed. To this mixture, 130.20 parts ammonium sulfate, 9.83 parts citricacid, and 13.17 parts of 2% EDTA were added and mixed. The pH of themixture was about 3.3. The vessel was sealed and sparged with nitrogenfor 30 minutes, and then polymerization was started by adding 7.53 partsof 1% V-50. The reaction mixture was heated to 40° C. for 2 hours andthen raised to and held at 50° C. for 4 hours. The overall conversionwas greater than 99%. A stable fluid aqueous dispersion was obtained.The bulk viscosity of this dispersion was about 760 cps as measured witha Brookfield Viscometer No. 4 spindle, 30 rpm at 25° C. showingpreferable fluidity. The dispersion was dissolved to give a SV of 2.52cps.

EXAMPLE 38A

A suitable vessel with an external jacket for heating or cooling wasequipped with a mechanical stirrer, reflux condenser, thermocouple andnitrogen inlet tube. The vessel was charged with 343.7 parts deionizedwater and 63.8 parts of 49% aqueous solution of polyamine (condensationproduct of dimethylamine and epichlorohydrin with low amountmultiamine), weight average molecular weight about 344,000. Aftercompletion of dissolution, 93.47 parts of a 52.8% aqueous solution ofacrylamide and 174 parts of an 79.2% aqueous solution of DEAEA.DMS wereadded and mixed. To this mixture, 130.2 parts ammonium sulfate, 10.25parts citric acid, 7.6 parts glycerol, and 13.1 parts of 2% EDTA wereadded and mixed. The pH of the mixture was about 3.2. The vessel wassealed and sparged with nitrogen for about 30 minutes, and thenpolymerization was started by adding 3.93 parts of 2% V-50 at about 48°C. The reaction mixture was held at this temperature for 5 hours. Theoverall conversion was greater than 99%. A stable fluid aqueousdispersion was obtained. The bulk viscosity of this dispersion was about1020 cps as measured with a Brookfield viscometer No. 4 spindle, 30 rpmat 25° C. showing preferable fluidity. The dispersion was dissolved togive a SV of 3.57 cps.

EXAMPLE 39

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 63.18 partsdeionized water and 30.8 parts of 40% aqueous solution ofpoly(DMAEM.MeCl), weight average molecular weight about 230,600. Aftercompletion of dissolution, 27.96 parts of a 53.33% aqueous solution ofacrylamide (AMD), 26.02 parts of a 80% aqueous solution of DEAEA.DMS and16.94 parts of a 80% aqueous solution of the methyl chloride quaternarysalt of dimethylaminoethylacrylate (DMAEA.MeCl) were added and mixed. Tothis mixture, 40.7 parts ammonium sulfate, 2.57 parts citric acid, and6.9 parts of 1% EDTA were added and mixed. The pH of the mixture wasabout 3.3. The vessel was sealed and sparged with nitrogen for 30minutes, and then polymerization was started by adding 4.93 parts of 1%V-50. The reaction mixture was raised to 40° C. for 2 hours, and thenraised to and held at 50° C. for 4 hours. The overall conversion wasgreater than 99%. A stable fluid aqueous dispersion was obtained. Thebulk viscosity of this dispersion was about 3840 cps as measured with aBrookfield Viscometer, No. 4 spindle, 30 rpm at 25° C. showing goodfluidity. The dispersion was dissolved to give a SV of 2.14 cps.

EXAMPLE 39A

A suitable vessel with an external jacket for heating or cooling wasequipped with a mechanical stirrer, reflux condenser, thermocouple andnitrogen inlet tube. The vessel was charged with 88.37 parts deionizedwater and 22.1 parts of 49% aqueous solution of polyamine (condensationproduct of dimethylamine and epichlorohydrin with low amountmultiamine), weight average molecular weight about 344,000. Aftercompletion of dissolution, 30.9 parts of a 53% aqueous solution ofacrylamide and 18.62 parts of an 79.2% aqueous solution of DEAEA.DMS and28.9 parts of an 80% aqueous solution of DMAEA.MeCl were added andmixed. To this mixture, 47.5 parts ammonium sulfate, 3.05 parts citricacid, 2.2 parts glycerol, and 3.8 parts of 0.5% EDTA were added andmixed. The pH of the mixture was about 3.2. The vessel was sealed andsparged with nitrogen for 30 minutes, and then polymerization wasstarted by adding 4.55 parts of 2% V-50 at about 48° C. The reactionmixture was held at this temperature for 5 hours. The overall conversionwas greater than 99%. A stable fluid aqueous dispersion was obtained.The bulk viscosity of this dispersion was about 2560 cps as measuredwith a Brookfield viscometer No. 4 spindle, 30 rpm at 25° C. showingpreferable fluidity. The dispersion was dissolved to give a SV of 3.44cps.

EXAMPLES 40-42

Polymerizations were carried out in the same manner as Example 39 exceptthat the bulk viscosity was adjusted by varying the level of ammoniumsulfate salt as shown in Table 3. These Examples demonstrate thataqueous dispersions having low bulk viscosities and high polymer solidsmay be prepared, wherein the first cationic polymer is aDMAEA.MeCl/DEAEA.DMS/AMD terpolymer.

TABLE 3 EXAM- FIRST SECOND PLE % TOTAL POLYMER POLYMER % BV SV NO.SOLIDS % SOLIDS % SOLIDS SALT (cps) (cps) 39 28 22.4 5.6 18.5 2,620 2.9940 28 22.4 5.6 18 4,310 2.96 41 28 22.4 5.6 19 1,820 2.65 42 28 22.4 5.619.5 2,000 2.62

EXAMPLE 43

A suitable vessel equipped with an external jacket for heating orcooling, a mechanical stirrer, reflux condenser, thermocouple andnitrogen inlet tube was charged with 260.35 parts deionized water and117.6 parts of a 40% aqueous solution of poly(DMAEM.MeCl), weightaverage molecular weight about 210,000. After completion of dissolution,107.89 parts of a 52.77% aqueous solution of acrylamide, 99.35 parts ofa 80% aqueous solution of DEAEA.DMS and 64.68 parts of a 80% aqueoussolution of DMAEA.MeCl were added and mixed. To this mixture, 271.92parts ammonium sulfate, 9.83 parts citric acid, and 13.17 parts of 2%EDTA were added and mixed. The pH of the mixture was about 3.3. Thevessel was sealed and sparged with nitrogen for 30 minutes, and thenpolymerization was started by adding 7.53 parts of 2.5% V-50. Thereaction mixture was raised to 40° C. for 2 hours, and then raised toand held at 50° C. for 4 hours. The overall conversion was greater than99%. A stable fluid aqueous dispersion was obtained. The bulk viscosityof this dispersion was about 1240 cps as measured with a BrookfieldViscometer, No. 4 spindle, 30 rpm at 25° C. showing good fluidity. Thedispersion was dissolved to give a SV of 2.74 cps.

EXAMPLE 44

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and nitrogen inlet tube was charged with 18.86 parts deionized water and9 parts of a 40% aqueous solution of poly(DMAEM.MeCl), weight averagemolecular weight about 200,000. After completion of dissolution, 4.39parts of a 53.64% aqueous solution of acrylamide and 15.19 parts of a79.3% aqueous solution of DEAEA.DMS were added and mixed. To thismixture, 8.4 parts ammonium sulfate, 0.7 parts citric acid, and 2.02parts of 1% EDTA were added and mixed. The pH of the mixture was about3.3. The vessel was sealed and sparged with nitrogen for 30 minutes, andthen polymerization was started by adding 1.44 parts of 1% V-50. Thereaction mixture was raised to 40° C. for 2 hours and then raised to andheld at 50° C. for 8 hours. The conversion was greater than 99%. Astable fluid aqueous dispersion was obtained. The bulk viscosity of thisdispersion was about 850 cps as measured with a Brookfield Viscometer,No. 4 spindle, 30 rpm at 25° C. showing preferable fluidity. Thedispersion was dissolved to give a SV of 2.27 cps.

EXAMPLES 45-49

Additional aqueous dispersions were prepared in the same manner asExample 44, demonstrating the effect of ratio of first cationic tosecond cationic polymer and salt content on the bulk viscosity of thedispersion as shown in Table 4.

TABLE 3 EXAM- FIRST SECOND PLE % TOTAL POLYMER POLYMER % BV SV NO.SOLIDS % SOLIDS % SOLIDS SALT (cps) (cps) 44 30 24 6 14   852 2.27 45 3024 6 12 2,400 2.19 46 30 24 6 13 1,100 2.34 47 30 24 6 15 1,770 2.35 4830 25 5 13 1,260 2.45 49 30 25 5 14 4,750 2.4 50 30 24  6* 14   780 2.2*Molecular weight of second polymer was about 222,600.

EXAMPLE 51

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and nitrogen inlet tube was charged with 92.9 parts deionized water and30.1 parts of a 41% aqueous solution of poly(DMAEM.MeCl), weight averagemolecular weight about 395,000. After completion of dissolution, 15.03parts of a 53.57% aqueous solution of acrylamide and 51.53 parts of an80% aqueous solution of DEAEA.DMS were added and mixed. To this mixture22 parts of sodium sulfate, 2.57 parts citric acid, and 3.45 parts of 2%EDTA were added mixed. The pH of the mixture was about 3.3. The vesselwas sealed and sparged with nitrogen for 30 minutes, and thenpolymerization was started by adding 2.46 parts of 2% V-50. The reactionmixture was raised to 40° C. for 2 hours and then raised to and held at50° C. for 4 hours. The overall conversion was greater than 99%. Astable fluid aqueous dispersion was obtained. The bulk viscosity of thisdispersion was about 1100 cps as measured with a Brookfield Viscometer,No. 4 spindle, 30 rpm at 25° C. The dispersion was dissolved to give aSV of 2.19 cps. This Example demonstrates the effectiveness of sodiumsulfate.

EXAMPLE 52

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 17.57 partsdeionized water and 9 parts of a 40% aqueous solution ofpoly(DMAEM.MeCl), weight average molecular weight about 200,000. Aftercompletion of dissolution, 4.77 parts of a 53.64% aqueous solution ofacrylamide, 12 parts of a 79.3% aqueous solution of DEAEA.DMS and 2.91parts of an 80% aqueous solution of DMAEA.MeCl were added and mixed. Tothis mixture, 9.6 parts ammonium sulfate, 0.7 parts citric acid, and2.02 parts of 1 % EDTA were added and mixed. The pH of the mixture wasabout 3.3. The vessel was sealed and sparged with nitrogen for 30minutes, and then polymerization was started by adding 1.44 parts of 1%V-50. The reaction mixture was raised to 40° C. for 2 hours and thenraised to and held at 50° C. for 4 hours. The overall conversion wasgreater than 99%. A stable fluid aqueous dispersion was obtained. Thebulk viscosity of this dispersion was about 800 cps as measured with aBrookfield Viscometer, No. 4 spindle, 30 rpm at 25° C. showing goodfluidity. The dispersion was dissolved to give a SV of 2.3 cps.

EXAMPLES 53-80

Polymerizations were carried out in the same manner as Example 52. Theeffect of total polymer solids, first cationic polymer composition (interms of % AMD, % DEAEA.DMS and % DMAEA.MeCl in monomer feed), ratio offirst cationic to second cationic polymer, and ammonium sulfate saltcontent on the bulk viscosity of the aqueous dispersion is demonstratedas shown in Table 5.

TABLE 5 FIRST SECOND % % % % TOTAL POLYMER POLYMER % NO. AMD DEAEA.DMSDMAEA.MeCl SOLIDS % SOLIDS % SOLIDS SALT BV (cps) SV (cps) 52 45 40 1530 24 6 16 802 2.3 53 45 40 15 30 24 6 12 200,000+ 2.4 54 45 40 15 30 246 13 30,900 2.35 55 45 40 15 30 24 6 14 4,410 2.35 56 45 40 15 30 24 615 1,080 2.42 57 45 40 15 30 24 6 17 1,820 2.32 58 45 40 15 30 24 6 1815,800 2.2 59 45 40 15 30 24 6 19 200,000+ 60 45 40 15 30 25 5 15 1,9402.45 61 45 40 15 30 25 5 16 1,260 2.49 62 45 40 15 30 25 5 17 6,010 2.463 45 35 20 30 24 6 15 3,120 2.19 64 45 35 20 30 24 6 16 1,340 2.24 6545 35 20 30 24 6 17 1,140 2.32 66 45 30 25 30 24 6 16 170,000 1.82 67 4530 25 30 24 6 17 1,890 2.44 68 45 30 25 30 24 6 18 1,400 2.35 69 45 2035 29.3 23.44 5.86 18 200,000+ 70 45 20 35 29.3 23.44 5.86 18.5 2,9002.4 71 45 20 35 29.3 23.44 5.86 19 6,600 2.24 72 45 10 45 28.5 22.8 5.718 200,000+ 2.35 73 45 10 45 28.5 22.8 5.7 19 200,000+ 2.34 74 45 10 4528 22.4 5.6 19.6 200,000+ 2.5 75 45 20 35 29 23.2 5.8 18 200,000+ 2.2 7645 20 35 29 23.2 5.8 18.5 5,540 2.27 77 45 20 35 29 23.2 5.8 19 3,5702.47 78 45 20 35 28.5 23.2 5.8 18 6,350 2.35 79 45 20 35 28.5 23.2 5.818.5 3,060 2.4 80 45 20 35 28.5 23.2 5.8 19 200,000+ 2.39

EXAMPLE 81

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 89 parts deionizedwater and 20.9 parts of a 40% aqueous solution of poly(DMAEM.MeCl),weight average molecular weight about 190,000. After completion ofdissolution, 30.96 parts of a 52.77% aqueous solution of acrylamide and21.38 parts of a 80% aqueous solution of DEAEA.DMS were added and mixed.To this mixture, 49.5 parts ammonium sulfate, 2.57 parts citric acid,and 2.34 parts of 1% EDTA were added and mixed. The pH of the mixturewas about 3.3. The vessel was sealed and sparged with nitrogen for 30minutes, and then polymerization was started by adding 3.34 parts of 1%V-50. The reaction mixture was raised to 40° C. for 2 hours and thenraised to and held at 50° C. for 4 hours. The combined conversion wasgreater than 99%. A stable fluid aqueous dispersion was obtained. Thebulk viscosity of this dispersion was about 280 cps as measured with aBrookfield Viscometer, No. 4 spindle, 30 rpm at 25° C. showing goodfluidity. The dispersion was dissolved to give a SV of 1.60 cps.

EXAMPLES 82-97

Polymerizations were carried out in the same manner as Example 81. Theeffect of chelant (EDTA) concentration, chain transfer agent (lacticacid), first cationic polymer composition (in terms of % AMD, %DEAEA.DMS, and % DMAEA.MeCl in monomer feed), ratio of first cationic tosecond cationic polymer, and ammonium sulfate salt content on standardviscosity and bulk viscosity are demonstrated as shown in Table 6.

TABLE 6 % FIRST SECOND % % % % TOTAL POLYMER POLYMER LACTIC EDTA % BV SVNO. AMD DEAEA.DMS DMAEA.MeCl SOLIDS % SOLIDS % SOLIDS ACID (ppm) SALT(cps) (cps) 81 80 20 19 15.2 3.8 0 1400 22.5 280 1.6 82 80 20 20 16 4 01400 20 142,000    1.82 83 80 20 20 16 4 0 1400 22.5 840 1.6 84 80 20 1915.2 3.8 0.25 1400 22.5 200 2.05 85 80 20 19 15.2 3.8 0.5 1400 22.5 1001.67 86 80 20 19 15.2 3.8 0.75 1400 22.5 200 1.87 87 80 20 19 15.2 3.8 02000 22.5 280 1.61 88 80 20 19 15.2 3.8 0 3000 22.5 4,800   1.81 89 8020 19 15.2 3.8 0.25 2000 22.5 270 1.99 90 80 20 19 15.2 3.8 0.5 200022.5 2,000   2.47 91 80 20 19 15.2 3.8* 0.5 2000 22.5 140 2.1 92 80 2019 15.2 3.8 0.5 2000 22.5 640 2.45 93 80 20 19 15.2 3.8 0.65 2000 22.5360 2.4 94 80 20 19 15.2 3.8 0.75 2000 22.5 225 2.35 95 80 10 10 19 15.23.8 0 1400 22.5 760 2.09 96 80 10 10 19 15.2 3.8 0.25 1400 22.5 460 2.8697 80 10 10 19 15.2 3.8 0.5 1400 22.5 340 2.74 *Molecular weight ofsecond polymer was about 222,600.

EXAMPLE 98

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 87.97 partsdeionized water and 20.9 parts of a 40% aqueous solution ofpoly(DMAEM.MeCl), weight average molecular weight about 190,000. Aftercompletion of dissolution, 33.99 parts of a 52.77% aqueous solution ofacrylamide, 11.74 parts of a 80% aqueous solution of DEAEA.DMS and 7.64parts of a 80% aqueous solution of DMAEA.MeCl were added and mixed. Tothis mixture, 49.5 parts ammonium sulfate, 2.57 parts citric acid, and2.34g of 2% EDTA were added and mixed. The pH of the mixture was about3.3. The vessel was sealed and sparged with nitrogen for 30 minutes, andthen polymerization was started by adding 2.34 parts of 1% V-50. Thereaction mixture was raised to 40° C. for 2 hours and then raised to andheld at 50° C. for 4 hours. The overall conversion was greater than 99%.A stable fluid aqueous dispersion was obtained. The bulk viscosity ofthis dispersion was about 760 cps as measured with a BrookfieldViscometer, No. 4 spindle, 30 rpm at 25° C. The dispersion was dissolvedto give a SV of 2.09 cps.

EXAMPLES 99-100

Polymerizations were carried out in the same manner as Example 97. Theeffect of chain transfer agent (lactic acid) concentration on bulkviscosity is demonstrated as shown in Table 7.

TABLE 7 FIRST SECOND LACTIC EXAMPLE % TOTAL POLYMER POLYMER ACID % BVNO. SOLIDS % SOLIDS % SOLIDS % SALT (cps) SV (cps) 98 19 15.2 3.8 0 22.5760 2.09 99 19 15.2 3.8 0.25 22.5 460 2.86 100 19 15.2 3.8 0.5 22.5 3402.74

EXAMPLE 101

A suitable vessel equipped with a mechanical stirrer, reflux condenser,thermocouple and nitrogen inlet tube was charged with 82.15 partsdeionized water and 30.8 parts of a 20% aqueous solution ofpoly(diallyldimethylammonium chloride) (poly(DADMAC)), weight averagemolecular weight about 289,000. After completion of dissolution, 48.24parts of a 52.77% aqueous solution of acrylamide and 13.27 parts of an80% aqueous solution of DEAEA.DMS were added and mixed. To this mixture,49.5 parts ammonium sulfate, 2.57 parts citric acid, 1.67 parts of 10%lactic acid, and 3.34 parts of 2% EDTA were added and mixed. The pH ofthe mixture was about 3.3. The vessel was sealed and sparged withnitrogen for 30 minutes, and then polymerization was started by adding3.34 parts of 1% V-50. The reaction mixture was raised to 40° C. for 2hours and then raised to and held at 50° C. for 4 hours. The combinedconversion was greater than 99%. A stable fluid aqueous dispersion wasobtained. The bulk viscosity of this dispersion was about 960 cps asmeasured with a Brookfield Viscometer, No. 4 spindle, 30 rpm at 25° C.showing preferable fluidity. The dispersion was dissolved to give a SVof 3.67 cps. This Example demonstrates aqueous dispersions havingpoly(DADMAC) as the second cationic polymer.

EXAMPLE 101A

A suitable vessel with an external jacket for heating or cooling wasequipped with a mechanical stirrer, reflux condenser, thermocouple andnitrogen inlet tube. The vessel was charged with 381.3 parts deionizedwater and 30.9 parts of 49% aqueous solution of polyamine (condensationproduct of dimethylamine and epichlorohydrin with low amountmultiamine), weight average molecular weight about 344,000. Aftercompletion of dissolution, 156.3 parts of a 52.08% aqueous solution ofacrylamide and 47.83 parts of an 79.2% aqueous solution of DEAEA.DMSwere added and mixed. To this mixture, 193.2 parts ammonium sulfate,10.25 parts citric acid, 7.16 parts glycerol, and 11.93 parts of 2% EDTAwere added and mixed. The pH of the mixture was about 3.2. The vesselwas sealed and sparged with nitrogen for 30 minutes, and thenpolymerization was started by adding 1.19 parts of 2% V-50 at about 48°C. The reaction mixture was held at this temperature for 5 hours. Theoverall conversion was greater than 99%. A stable fluid aqueousdispersion was obtained. The bulk viscosity of this dispersion was about640 cps as measured with a Brookfield viscometer No. 4 spindle, 30 rpmat 25° C. showing preferable fluidity. The dispersion was dissolved togive a SV of 4.5 cps. This Example demonstrates aqueous dispersionshaving polyamine as the second polymer.

EXAMPLE 102

A suitable vessel equipped with an external jacket for heating orcooling, mechanical stirrer, reflux condenser, thermocouple and nitrogeninlet tube was charged with 262.6 parts deionized water, 47.4 parts of a40% aqueous solution of poly(DMAEM.MeCl), weight average molecularweight about 41,500, and 92.60 parts of a 40% aqueous solution ofpoly(DMAEM.MeCl), weight average molecular weight about 205,000. Aftercompletion of dissolution, 88.1 parts of a 53.12% aqueous solution ofacrylamide and 133.9 parts of a 72.6% aqueous solution of the methylchloride quaternary salt of diethylaminoethylacrylate (DEAEA.MeCl) wereadded and mixed. To this mixture, 144 parts ammonium sulfate, 2.644parts citric acid, and 14.4 parts of 1% EDTA were added and mixed. ThepH of the mixture was about 3.3. The vessel was sealed and sparged withnitrogen for 30 minutes, and then polymerization was started by adding14.4 parts of 2% V-50. The reaction mixture was raised to and held at40-45° C. for 6 hours. The conversion was greater than 99.9%. A stablefluid aqueous dispersion was obtained. The bulk viscosity of thisdispersion was about 2,200 cps as measured with a Brookfield Viscometer,No. 4 spindle, 30 rpm at 25° C. The dispersion was dissolved to give aSV of 3.31 cps. This Example demonstrates an aqueous dispersion having athird cationic polymer.

EXAMPLE 103

Polymerization was carried out in the same manner as Example 102, exceptthat the two poly(DMAEM.MeCl) polymers were replaced with a singlepoly(DMAEM.MeCl) having a weight average molecular weight of about1,500,000. The bulk viscosity of this dispersion was about 8,000 cps asmeasured with a Brookfield Viscometer, No. 4 spindle, 30 rpm at 25° C.showing preferable fluidity. The dispersion was dissolved to give a SVof 2.45 cps.

EXAMPLE 104

A suitable vessel equipped with an external jacket for heating,mechanical stirrer, reflux condenser, thermocouple and nitrogen inlettube was charged with 23.8 parts deionized water and 25.3 parts of a 20%aqueous solution of poly(DADMAC), weight average molecular weight about289,000. After completion of dissolution, 7.9 parts of a 53.1% aqueoussolution of acrylamide and 11.3 parts of a 77.9% aqueous solution ofDEAEA.MeCl were added and mixed. To this mixture, 18 parts ammoniumsulfate, 1.08 parts citric acid, 0.37 part of 5% EDTA, and 0.9 partglycerol were added and mixed. The pH of the mixture was about 3.3. Thevessel was sealed and sparged with nitrogen for 30 minutes, and thenpolymerization was started by adding 1.3 parts of I% V-50 at 40° C. Thistemperature was held for 2 hours and then was raised to 50° C. andmaintained at this temperature for 8 hours. The residual acrylamidelevel was about 209 parts per million (ppm). A stable fluid aqueousdispersion was obtained. The bulk viscosity of this dispersion was about2,950 cps as measured with a Brookfield Viscometer, No. 4 spindle, 30rpm at 25° C. showing preferable fluidity. The dispersion was dissolvedto give a SV of 2.47 cps.

EXAMPLES 105-108

Polymerizations were carried out in the same manner as Example 104,except that part of the poly(DADMAC) was replaced with a poly(DADMAC)polymer having a lower weight average molecular weight. The effect onthe aqueous dispersion bulk viscosity of including the third polymer isshown in Table 8.

TABLE 8 % FIRST SECOND SECOND THIRD THIRD TOTAL POLYMER POLYMER POLYMERPOLYMER POLYMER % BV SV NO. SOLIDS % SOLIDS % SOLIDS MW % SOLIDS MW SALT(cps) (cps) 104 21.2 14.5 5.06 289,000 20 2,950 2.47 105 21.2 14.5 3.73289,000 1.89 10,100 20 2,200 2.4 106 21.2 14.5 3.73 289,000 1.89 53,40020 1,950 2.4 107 21.2 14.5 3.73 289,000 1.89 67,900 20 2,020 2.39 10821.2 14.5 3.73 289,000 1.89 100,000  20 1,990 2.42

EXAMPLE 109

An aqueous dispersion containing 12.5% ammonium sulfate and having apolymer solids of 30%, a bulk viscosity of about 7200 cps and a standardviscosity of about 2.34 cps was prepared in the same manner as inExample 2.

EXAMPLE 110

An aqueous dispersion containing 15.5% ammonium sulfate and having apolymer solids level of 28%, a bulk viscosity of about 2640 cps and astandard viscosity of about 2.4 cps was prepared in the same manner asin Example 9.

EXAMPLES 111-133

Various amounts of either ammonium sulfate, sodium thiocyanate, or1,3-benzenedisulfonate (1,3-BDS) were added to the base aqueousdispersions of Example 109, Example 110, Example 103, Example 1, Example102 and Example 142. The bulk viscosities of the resultant aqueousdispersions were further reduced as shown in Table 9. These Examplesdemonstrate that the bulk viscosity of aqueous dispersions may bereduced by adding salt to the dispersion, and that the addition of1,3-BDS may be more effective than ammonium sulfate on a weight basis.Substantially similar results are obtained by polymerizing the monomersin the presence of the salts.

TABLE 9 Ex- am- Base BV of Base % ple Aqueous Aqueous Total % Total BVNo. Dispersion Dispersion Added Salt Salt Solids (cps) 111 Example 1097200 (NH₄)₂SO₄ 14.21 29.41 2100 112 Example 109 7200 (NH₄)₂SO₄ 15.8628.84 1,000 113 Example 109 7200 (NH₄)₂SO₄ 17.45 28.3 501 114 Example109 7200 (NH₄)₂SO₄ 19 27.8 319 115 Example 109 7200 1,3-BDS 13.37 29.72200 116 Example 109 7200 1,3-BDS 14.21 29.41 1160 117C Example 109 72001,3-BDS 15 29.12 FL 118 Example 110 2640 NaSCN 16.3 27.7 540 119CExample 110 2640 NaSCN 17.15 27.45 FL 120C Example 110 2640 NaSCN 17.9627.18 FL 121 Example 103 8000 1,3-BDS 19.6 24.51 1660 122 Example 1038000 1,3-BDS 21.15 24.04 762 123 Example 103 8000 1,3-BDS 22.64 23.58 FL124 Example 103 8000 (NH₄)₂SO₄ 19.6 24.51 3440 125 Example 103 8000(NH₄)₂SO₄ 21.15 24.04 1990 126 Example 103 8000 (NH₄)₂SO₄ 22.64 23.581300 127 Example 103 8000 (NH₄)₂SO₄ 24.07 23.15 982 128 Example 1 2300(NH₄)₂SO₄ 19 27.8 501 129 Example 102 2200 (NH₄)₂SO₄ 19.6 24.51 1002 130Example 102 2200 (NH₄)₂SO₄ 21.15 14.04 441 131 Example 102 2200(NH₄)₂SO₄ 22.64 23.58 301 132 Example 102 2200 (NH₄)₂SO₄ 24.07 23.15 200133 Example 142 10,000 (NH₄)₂SO₄ 24.07 23.15 1380 C: Comparative FL:Formed Layers

EXAMPLE 134

About 18 parts of the aqueous dispersion of Example 49 and about 20parts of the aqueous dispersion of Example 91 were intermixed withstirring. The resultant aqueous dispersion blend was stable and veryuniform with a bulk viscosity of about 880 cps, demonstrating thatdifferently charged dispersions may be blended to prepare an aqueousdispersion having an intermediate charge. The aqueous dispersion blendhad an overall charge of about 40% and a SV of 2.5 cps.

EXAMPLE 135

About 18 parts of a high charge aqueous dispersion prepared as inExample 48 and about 18 parts of a low charge aqueous dispersionprepared as in Example 101 were intermixed with stirring. The resultantaqueous dispersion blend was stable and very uniform with a bulkviscosity of about 2300 cps, demonstrating that differently chargeddispersions may be blended to prepare an aqueous dispersion having anintermediate charge. The resultant aqueous dispersion contained fourdifferent polymers.

EXAMPLE 136 Comparative

A polymerization was conducted in the same manner as Example 9, exceptthat the DEAEA.DMS was replaced with an equal weight of DMAEA.MeCl.During the process of polymerization, the contents of the vessel becameso viscous that stirring became impossible. The product was obtained asa gel without fluidity. This Example demonstrates that replacement ofDMAEA.MeCl with DEAEA.DMS results in an aqueous dispersion having adramatically lower bulk viscosity.

EXAMPLE 137 Comparative

A polymerization was conducted in the same manner as Example 50, exceptthat the DEAEA.DMS was replaced with an equal weight of DMAEA.MeCl.During the process of polymerization, the contents of the vessel becameso viscous that stirring became impossible. The product was obtained asa gel without fluidity. This Example demonstrates that replacement ofDMAEA.MeCl with DEAEA.DMS results in an aqueous dispersion having adramatically lower bulk viscosity.

EXAMPLE 138 Comparative

A polymerization was conducted in the same manner as Example 91, exceptthat the DEAEA.DMS was replaced with an equal weight of DMAEA.MeCl.During the process of polymerization, the contents of the vessel becameso viscous that stirring became impossible. The product was obtained asa gel without fluidity. This Example demonstrates that replacement ofDMAEA.MeCl with DEAEA.DMS results in an aqueous dispersion having adramatically lower bulk viscosity.

EXAMPLE 139 Comparative

A polymerization was conducted in the same manner as Example 100, exceptthat the DEAEA.DMS was replaced with an equal weight of DMAEA.MeCl.During the process of polymerization, the contents of the vessel becameso viscous that stirring became impossible. The product was obtained asa gel without fluidity. This Example demonstrates that replacement ofDMAEA.MeCl with DEAEA.DMS results in an aqueous dispersion having adramatically lower bulk viscosity

EXAMPLE 140

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and nitrogen inlet tube was charged with 20 parts deionized water and10.51 parts of a 40% aqueous solution of poly(DMAEM.MeCl), weightaverage molecular weight about 210,000. After completion of dissolution,6.57 parts of a 53.27% aqueous solution of acrylamide, 14.56 parts of an80% aqueous solution of DMAEA.MeCl and 4.15 parts of a 80% aqueoussolution of DMAEA.BzCl were added and mixed. To this mixture, 10.8 partsammonium sulfate, 0.4 parts citric acid, and 1.51 parts of 1% EDTA wereadded and mixed. The pH of the mixture was about 3.3. The vessel wassealed and sparged with nitrogen for 30 minutes, and then polymerizationwas started by adding 1.08 parts of 1% V-50. The reaction mixture wasraised to 40° C. 2 hours by placing the vessel in a water bath and thenraised to 50° C. for 6 hours. The conversion was greater than 99%. Astable fluid aqueous dispersion was obtained. The bulk viscosity of thisdispersion was about 2000 cps showing preferable fluidity as measuredwith a Brookfield Viscometer No. 4 spindle, 30 rpm at 25° C. Thedispersion was dissolved to give a SV of 2.2 cps.

EXAMPLES 141-144

Polymerizations were carried out in the same manner as Example 140. Theeffect of the composition of the first polymer (given in terms of % AMD,% DMAEA.MeCl, and DMAEA.BzCl in monomer feed) and molecular weight ofthe poly(DMAEM.MeCl) on the aqueous dispersion bulk viscosity is shownin Table 10.

TABLE 10 FIRST SECOND SECOND % % % % TOTAL POLYMER POLYMER POLYMER % NO.AMD DMAEA.MeCl DMAEA.BzC SOLIDS % SOLIDS % SOLIDS MW SALT BV (cps) SV(cps) 140 60 25 15 25 18 7 210,000 18  2,000 2.2 141 60 25 15 25 18 7500,000 18 13,200 2.34 142 60 25 15 25 18 7 1,500,000  18 10,000 2.4 14360 25 15 25 18 7 800,000 18 11,500 2.2 144 60 29.2 10.8 25 19 6 200,00018 8,680 2.59

EXAMPLES 145-150 Comparative

Polymerizations were carried out in the same manner as Example 140 atdifferent ratios of AMD/DMAEA.MeCl/DMAEA.BzCl/DEAEA.DMS except that thepoly(DMAEM.MeCl) was omitted. During the polymerization process, thecontents of the vessel became very viscous to the point that stirringbecame impossible. The resulting polymerization product was obtained asa clear gel, a homogeneous composition without ity as shown in Table 11.

TABLE 11 % % % % % NO. AMD DMAEA.MeCl DMAEA.BzCl DEAEA.DMS SOLIDS SALTBV (cps) 145C 50 40 10 14.4 20 Gel 146C 45 40 15 14.4 20 Gel 147C 6029.2 10.8 18 18 Gel 148C 60 25 15 18 18 Gel 149C 55 5 40 18 18 Gel 150C55 5 40 25 18 Gel C: Comparative

EXAMPLES 151-153

An aqueous dispersion having a bulk viscosity of about 3570 cps wasprepared in the same manner as Example 13. The dispersion wasconcentrated by placing about 135 parts into a suitable vessel andheating to 45° C. under flowing nitrogen. A total of 26 parts of waterwas removed in two stages by this dehydration process. The aqueousdispersion remained stable demonstrating that dehydration is effectivefor achieving high solids, low bulk viscosity aqueous dispersions asshown in Table 12.

TABLE 12 Polymer Bulk Example No. Solids (%) Viscosity (cps) 151 (aspolymerized) 28.0 3570 152 31.5  660 153 34.6 3260

EXAMPLE 154

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and a nitrogen inlet tube was charged with 277.75 parts deionized waterand 112.0 parts of a 40% aqueous solution of poly(DMAEM.MeCl), weightaverage molecular weight about 200,000. After completion of dissolution,89.03 parts of a 53.64% aqueous solution of acrylamide, and 164.93 partsof an 80% solution of DEAEA.DMS were added and mixed. To this mixture,124.0 parts ammonium sulfate, 9.36 parts citric acid, and 5.02 parts ofa 1% solution of EDTA were added and mixed. The pH of the mixture wasabout 3.3. The contents were heated to 48° C. and sparged with nitrogenfor 30 minutes, and then polymerization was started by adding 17.92parts of 1% aqueous solution of V-50. The reaction mixture wasmaintained at 48° C. for 5 hours. About 3.5 hours into thepolymerization the aqueous dispersion bulk viscosity began to noticeablyincrease. The final bulk viscosity of the aqueous dispersion was about8,000 cps as measured with a Brookfield Viscometer No. 4 spindle, 30 rpmat 25° C.

EXAMPLE 155-156

Duplicate polymerizations ware carried out in a similar manner toExample 154 except that an additional amount of ammonium sulfate (4% ontotal) was added approximately 3 hours after initiation ofpolymerization. This prevented any substantial increase in bulkviscosity during the polymerization and resulted in a final bulkviscosity that was lower than the bulk viscosity obtained in Example 154as shown in Table 13.

TABLE 13 Example No. Final Bulk Viscosity (#4 spindle, 30 rpm) 155 300cps 156 500 cps

EXAMPLES 157-172

General Polymerization Procedure: The following components were mixedtogether in a suitable vessel and the pH was adjusted to about 3.5 witha 28 wt. % solution of ammonium hydroxide.

Acrylamide (55.5 wt. %) 5.34 parts DEAEA.DMS (80 wt. %) 10.35 partsCitric acid 0.58 parts Ammonium sulfate 7.78 parts poly(DMAEM.MeCl) (40wt. %, 200,000 MW) 7.03 parts Deionized Water 16.22 parts V-50 (1 wt. %)1.12 parts EDTA (1 wt. %) 1.57 parts Methylenebisacrylamide (MBA)variable Lactic acid (chain transfer agent) variable

Forty parts of the solution were placed into a suitable vessel and thesolution was sparged with nitrogen. The vessel was sealed and placedinto a 40° C. water bath for 2 hours. The temperature was then increasedto 50° C. and maintained for an additional 3 hours. Results aresummarized in Table 14, showing that substantial levels of branchingagent and chain transfer agent can be incorporated into aqueousdispersions of water-soluble and water-swellable polymers. The aqueousviscosity values were obtained by dissolving or dispersing the aqueousdispersions in the same general manner as for the standard viscosityvalues described above, except that the polymer concentration was 0.135wt. %.

TABLE 14 Lactic acid MBA Dispersion bulk Ex. (wt. % (ppm on viscosity(#4 spindle, Aqueous No. on monomer) monomer) 30 rpm) Viscosity 157 0 0— 3.91 158 0.4 0 — 3.41 159 0.8 0 — 3.04 160 0 0 1100 3.71 161 0 2 10003.61 162 0 4 1600 3.66 163 0 6 2500 3.31 164 0 0 2200 3.11 165 0 10 33001.90 166 0 15 3300 1.77 167 0 20 8100 1.67 168 0 0 1200 2.81 169 0 301800 1.46 170 0 40 3500 1.43 171 0 50 — 1.44 172 0 100 — 1.28

EXAMPLE 173

A aqueous dispersion was prepared as in Example 155. The aqueousdispersion had a bulk viscosity of about 240 cps and an aqueousviscosity (obtained as in Examples 157-172) of 3.55 cps.

EXAMPLE 174

The aqueous dispersion of Example 173 was spray-dried on a commerciallyavailable laboratory spray dryer. The chamber of the laboratory spraydryer was 760 millimeters (mm) in diameter with a 860 mm vertical sideand a 65 degree conical bottom. Nominal gas flow through the dryer wasabout 180 cubic meters per hour. The aqueous dispersion feed was fed atthe center of the top of the chamber using a variable speed pump,through a two-fluid nozzle using air for atomization. The outlet gastemperature was 86 ° C. and controlled by varying the inlet gastemperature (169° C.) and the feed rate (60 milliliters/minute). Toprovide an inert atmosphere, the spray-dryer was supplied with nitrogengas from a cryogenic storage tank. The dried polymer product wasdischarged through the bottom of the dryer cone to a cyclone where thedry product was removed and collected. Residence time in the dryer wasabout 14 seconds. The resultant spray-dried polymer particles, which hada volatiles content of 3.4% and a bulk density of about 0.50 grams percubic centimeter (g/cc), were readily soluble in water and had a SV a3.49 cps.

EXAMPLE 175

The dissolution rate of the spray-dried polymer of Example 174 wascompared to a dry polymer of similar composition obtained byspray-drying a commercial water-in-oil emulsion. Solutions were preparedin a wide mouth quart jar using a 2.5 inch magnetic stirring bar. Thestirring rate was adjusted so that a deep vortex was obtained in thewater. The dry polymer was added slowly over a period of 5 minutes atthe edge of the vortex to avoid clumping. The spray-dried polymer ofExample 174 wet more readily and completely dissolved over a period of30-40 minutes, giving a clear solution. In contrast, the dry polymerobtained by spray-drying an inverse emulsion did not wet as rapidly andwas not completely dissolved after two hours. This Example demonstratesthat a dry polymer obtained by spray-drying an aqueous dispersion of theinstant invention dissolved faster than a dry polymer obtained byspray-drying a corresponding water-in-oil emulsion.

EXAMPLE 176C

The procedure of U.S. Pat. No. 5,403,883 Example 1 was followed. Adispersion having a bulk viscosity of about 10,600 cps (#4 spindle, 30rpm) was obtained.

EXAMPLE 177

The procedure of U.S. Pat. No. 5,403,883 Example 1 was followed, exceptthat the 2-trimethlyammoniumethyl acrylate chloride was replaced by anequal weight of DEAEA.MeCl. The resulting aqueous dispersion had a bulkviscosity of about 6,900 cps (#4 spindle, 30 rpm), demonstratingimproved bulk viscosity as compared to Example 176C.

EXAMPLE 178

A suitable vessel equipped with a mechanical stirrer, reflux condenser,and a nitrogen inlet tube was charged with 22.94 parts deionized waterand 10.5 parts of a 40% aqueous solution of poly(DMAEM.MeCl), weightaverage molecular weight about 245,000. After completion of dissolution,6.47 parts of a 54.20% aqueous solution of acrylamide, and 7.49 parts ofthe propyl chloride quaternary salt of dimethylaminoethyl acrylate wereadded and mixed. To this mixture, 10.8 parts ammonium sulfate, 0.7 partscitric acid, and 0.76 parts of a 2% solution of EDTA were added andmixed. The pH of the mixture was about 3.3. The vessel was sealed andsparged with nitrogen for 30 minutes, and then polymerization wasstarted by addition of 0.54 g of 2% aqueous solution of V-50. Thereaction mixture was heated to 40° C. for 2 hours and then raised to 50°C. and held for an additional 4 hours. The conversion was greater than99%. A stable fluid aqueous dispersion was obtained. The bulk viscosityof the aqueous dispersion was about 1300 cps showing preferable fluidityas measured with a Brookfield Viscometer, No. 4 spindle, 30 rpm at 25°C. The aqueous dispersion was dissolved to give a SV of 2.1 cps. ThisExample demonstrates that, despite Comparative Example 1 of EP 0 525 751A1, an aqueous dispersion may be formed when the first polymer containsrecurring units of the propyl chloride quaternary salt ofdimethylaminoethylacrylate.

EXAMPLE 179

An aqueous dispersion was prepared in a similar manner to Example 40except that the first polymer composition was AMD/DEAEA.DMS/DMAEA.MeCl(60/30/10 mole). The aqueous dispersion had a bulk viscosity of about3,600 cps (No. 4 spindle, 30 rpm at 25° C.) and a SV of 2.64 cps.

EXAMPLE 180

An aqueous dispersion was prepared in a similar manner to Example 40except that the first polymer composition was AMD/DEAEA.DMS/DMAEA.MeCl(60/25/15 mole). The aqueous dispersion had a bulk viscosity of about1,000 cps (No. 4 spindle, 30 rpm at 25° C.) and a SV of 2.87 cps.

EXAMPLE 180A-180E

Polymerizations were carried out in a similar manner to Example 39Aexcept that the bulk viscosity was adjusted by utilizing the salts shownin Table 14A. These examples demonstrate that aqueous dispersions havinglow bulk viscosities and high polymer solids may be prepared, where thefirst cationic polymer is DMAEA.MeCl/DEAEA.DMS/AMD (35/5/60 mole) andthe second polymer is polyamine, and that the viscosities may beadjusted with salts.

TABLE 14A First Second % % Total Polymer Polymer % Salt Salt BV SV Ex.Solids % Solids % Solids A B (cps) (cps) 180A 26 19.25 6.74 22.50 080,000 2.86 180B 26 18.57 7.43 22.50 0 10,700 2.70 180C 26 18.57 7.4319.35 3.15 10,200 3.24 180D 26 18.57 7.43 19.35 3.15  3,810 3.06 180E 2618.57 7.43 19.35 3.15  4,310 2.92 180A: Salt A = ammonium sulfate 180B:Salt A = ammonium sulfate 180C: Salt A = ammonium sulfate, Salt B =sodium nitrate 180D: Salt A = ammonium sulfate, Salt B = sodium chloride180E: Salt A = ammonium sulfate, Salt B = sodium sulfate

EXAMPLES 181-261

The performance of aqueous dispersions of the instant invention wasdetermined by measuring free drainage rate and cake solids fromdewatered sludge as follows: Two hundred grams of sewage sludge from amunicipal waste treatment plant were weighed into each of a series ofjars. Solutions of the aqueous dispersions and of W/O, a commercialwater-in-oil emulsion control (60/40 mole % AMD/DMAEA.MeCl), wereprepared so that the concentration of the polymer was about 0.2%.Various doses of the polymer solutions were intermixed with the sludgesamples and agitated at 500 rpm for 10 seconds (500 rpm/10 seconds) orat 1000 rpm for 5 seconds (1000 rpm/5 seconds) with an overhead mixer.The resultant aqueous mixture of flocculated sludge was dewatered bypouring it into a Buchner funnel containing a 35 mesh stainless steelscreen; the free drainage was determined by measuring the milliliters offiltrate collected in 10 seconds. Cake solids were determined by dryingthe pressed sludge at 105° C. The results are shown in Table 15, witheach polymer identified by previous Example No., free drainage in unitsof milliliters/10 seconds, mixing in rpm/seconds, dosage in units ofpounds of polymer per ton of dry sludge, and cake solids as a weightpercent of dry solids in wet cake. The notation “N/A” in the Table meansthat an accurate cake solids value could not be obtained. These Examplesshow that the performance of the aqueous dispersions of the instantinvention is substantially equivalent or superior to a comparablecommercial product.

TABLE 15 Free Cake No. Polymer Mixing Dosage Drainage Solids (%) 181 102500/10 24.4 137 17.3 182 102 500/10 26.7 140 16.9 183 102 500/10 28.9128 17.1 184 103 500/10 20 138 15.8 185 103 500/10 22.2 155 16.5 186 103500/10 24.4 158 16.5 187 103 500/10 26.7 162 15.7 188C W/O 500/10 24.4112 15.0 189C W/O 500/10 26.7 122 15.6 190C W/O 500/10 28.9 114 15.2 191102 1000/5 20.2 142 15.5 192 102 1000/5 22.2 145 15.8 193 102 1000/526.7 140 15.3 194 103 1000/5 24.4 130 15.7 195 103 1000/5 26.7 138 15.8196 103 1000/5 28.9 145 15.2 197C W/O 1000/5 22.2 112 16.0 198C W/O1000/5 24.4 120 16.2 199C W/O 1000/5 26.7 110 15.7 200 9 500/10 23 14416.6 201 9 500/10 27.2 160 17.0 202 9 500/10 31.4 140 17.1 203 179500/10 23 144 17.0 204 179 500/10 27.2 153 17.6 205 179 500/10 31.4 15217.4 206 180 500/10 23 100 16.9 207 180 500/10 27.2 130 16.8 208 180500/10 31.4 125 17.1 209C W/O 500/10 23 99 14.9 210C W/O 500/10 27.2 9215.2 211 9 1000/5 25.1 96 17.6 212 9 1000/5 29.3 97 18.0 213 9 1000/531.4 93 17.9 214 179 1000/5 29.3 107 17.7 215 179 1000/5 31.4 92 18.4216 179 1000/5 35.6 104 18.7 217 180 1000/5 25.1 84 16.9 218 180 1000/529.3 92 17.9 219 180 1000/5 31.4 136 17.1 220 180 1000/5 35.6 104 17.1221C W/O 1000/5 25.1 110 16.1 222C W/O 1000/5 29.3 112 16.5 223C W/O1000/5 31.4 108 16.8 224 44 500/10 22.1 140 17.5 225 44 500/10 24.5 13817.0 226 44 500/10 27 139 17.4 227 44 1000/5 22.1 120 19.0 228 44 1000/525.8 117 19.3 229 44 1000/5 29.4 104 19.5 230C W/O 500/10 18.4 108 NA231C W/O 500/10 22.1 110 NA 232C W/O 500/10 25.8 66 NA 233C W/O 1000/522.1 128 17.9 234C W/O 1000/5 25.8 102 17.6 235 61 500/10 16.9 130 17.2236 61 500/10 18.6 140 18.0 237 61 500/10 21.9 130 17.3 238 67 500/1015.2 80 16.8 239 67 500/10 16.9 105 17.8 240 67 500/10 18.6 126 18.2241C W/O 500/10 15.2 116 16.2 242C W/O 500/10 16.9 116 15.6 243C W/O500/10 18.8 82 15.4 244 140 500/10 26.5 138 18.0 245 140 500/10 29.4 14018.5 246 140 500/10 32.4 130 18.2 247 140 1000/5 29.2 118 17.8 248 1401000/5 32.4 129 18.4 249 140 1000/5 35.7 137 19.0 250 142 500/10 26.5120 16.9 251 142 500/10 29.4 142 17.2 252 142 500/10 32.4 127 17.1 253142 1000/5 25.9 120 17.3 254 142 1000/5 29.2 140 17.8 255 142 1000/532.4 138 18.3 256C W/O 500/10 14.7  76 14.0 257C W/O 500/10 17.6 11414.8 258C W/O 500/10 20.6 105 14.8 259C W/O 100015 22.7 104 16.8 260CW/O 1000/5 25.9 134 16.3 261C W/O 1000/5 29.2 113 16.7 C: ComparativeW/O: Commercially available water-in-oil emulsion copolymer ofacrylamide and DMAEA.MeCl (60/40 mole %)

EXAMPLES 262-263

The performance of the aqueous dispersions of Examples 118 and 121 isdetermined by measuring free drainage rate and cake solids fromdewatered sludge by following the procedure of Examples 181-261. Similarresults are obtained.

EXAMPLE 264

A solution of the spray-dried polymer of Example 174 is prepared so thatthe concentration of the polymer is about 0.2%. The performance isdetermined by measuring free drainage rate and cake solids fromdewatered sludge by following the procedure of Examples 181-261. Similarresults are obtained.

EXAMPLES 265-277

Solutions of the aqueous dispersions and spray-dried polymers ofExamples 9, 44, 61, 67, 102, 103, 118, 121, 140, 142, 174, 179, and 180are prepared so that the concentration of the polymer is about 0.2%. Theperformance is determined by measuring free drainage rate by followingthe procedure of Examples 181-261, except that a 1% suspension of papersolids is dewatered instead of sewage sludge. Similar results areobtained.

EXAMPLES 278-293

Aqueous admixtures are prepared by intermixing the aqueous dispersionsof Examples 157-172 with water so that the concentration of the polymeris about 0.2%. The performance is determined by measuring free drainagerate by following the procedure of Examples 181-261, except that a 1%suspension of paper solids is dewatered instead of sewage sludge.Similar results are obtained.

We claim:
 1. A composition comprised of an aqueous dispersion comprisedof: (a) a discontinuous phase containing polymer that is comprisedpredominately of a first cationic water-soluble or water-swellablepolymer having at least one first recurring unit of the formula (I),

wherein R₁ is H or CH₃, A is O or NH, B is an alkylene or branchedalkylene or oxyalkylene group having from 1 to 5 carbons, R₂ is amethyl, ethyl, or propyl group, R₃ is a methyl, ethyl, or propyl group,R₄ is a methyl, ethyl or propyl group, and X is a counterion; and (b) apolyamine.
 2. A composition as claimed in claim 1 wherein said R₂, R₃,and R₄ in said first recurring unit together contain a total of at least4 carbon atoms.
 3. A composition is claimed in claim 1 wherein saidaqueous dispersion is further comprised of an inorganic salt.
 4. Acomposition as claimed in claim 3 wherein said inorganic salt isselected from the group consisting of chlorides, sulfates, phosphates,hydrogenphosphates and mixtures thereof.
 5. A composition as claimed inclaim 1 wherein said R₂, R₃, and R₄ in said first recurring unittogether contain a total of at least 5 carbon atoms.
 6. A composition asclaimed in claim 1 wherein said first polymer is further comprised of arecurring anionic unit.
 7. A composition as claimed in claim 6 whereinsaid recurring anionic unit is selected from the group consisting ofacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid,styrenesulfonic acid, and salts thereof.
 8. A composition as claimed inclaim 1 wherein said first polymer is further comprised of a hydrophobicrecurring unit.
 9. A composition as claimed in claim 1 wherein saidfirst polymer is devoid of hydrophobic recurring units.
 10. Acomposition as claimed in claim 1, wherein said first polymer is furthercomprised of recurring (alk)acrylamide units.
 11. A composition asclaimed in claim 1, wherein said polyamine is formed from an amine andepihalohydrin or dihaloalkane.
 12. A composition as claimed in claim 1,wherein said first polymer is water-soluble and branched.
 13. Acomposition as claimed in claim 1, which is further comprised of a thirdwater-soluble or water-swellable polymer different from said firstpolymer or said polyamine.
 14. A composition as claimed in claim 1 whichis further comprised of a chaotropic salt selected from the groupconsisting of thiocyanates, iodides, bromides, nitrates, perchloratesand mixtures thereof.
 15. A composition as claimed in claim 1 which isfurther comprised of an anionic organic salt selected from the groupconsisting of aryl sulfonates having from 6 to 22 carbons, alkylsulfonates having from 2 to 22 carbons, and mixtures thereof.
 16. Acomposition as claimed in claim 1 which is further comprised of aviscosity-reducing additive.
 17. A composition comprising an aqueousdispersion comprised of: (a) a discontinuous phase containing polymerthat is comprised predominately of a first cationic water-soluble orwater-swellable polymer having at least one first recurring unit of theformula (I),

wherein R₁ is H or CH₃, A is O or NH, B is an alkylene or branchedalkylene or oxyalkylene group having from 1 to 5 carbons, R₂ is amethyl, ethyl, or propyl group, R₃ is a methyl, ethyl, or propyl group,R₄ is a methyl, ethyl or propyl group, X is a counterion, and R₂, R₃,and R₄ together contain a total of at least 4 carbon atoms; and (b) apolyamine.
 18. A composition as claimed in claim 17, wherein saidpolyamine is formed from an amine and epihalohydrin or dihaloalkane. 19.A composition as claimed in claim 17, wherein said aqueous dispersion isfurther comprised of ammonium sulfate.
 20. A composition as claimed inclaim 17 wherein said first polymer is further comprised of a recurringanionic unit.
 21. A composition as claimed in claim 20 wherein saidrecurring anionic unit is selected from the group consisting of acrylicacid, 2-acrylamido-2-methylpropane sulfonic acid, styrenesulfonic acid,and salts thereof.
 22. A composition as claimed in claim 17, which isfurther comprised of a third water-soluble or water-swellable polymerdifferent from said first polymer or said polyamine.
 23. A compositionas claimed in claim 17 which is further comprised of a chaotropic saltselected from the group consisting of thiocyanates, iodides, bromides,nitrates, perchlorates and mixtures thereof.
 24. A composition asclaimed in claim 17 which is further comprised of an anionic origanicsalt selected from the group consisting of aryl sulfonates having from 6to 22 carbons, alkyl sulfonates having from 2 to 22 carbons, andmixtures thereof.
 25. A composition as claimed in claim 17 which isfurther comprised of a viscosity-reducing additive.
 26. A composition asclaimed in claim 1, wherein, if said first polymer is further comprisedof a second recurring unit of formula (I) wherein R₁ is H or CH₃, A is Oor NH, B is an alkylene or branched alkylene or oxyalkylene group havingfrom 1 to 5 carbons, X is a counterion, and R₂, R₃ or R₄ is selectedfrom the group consisting of C₄-C₁₀ alkyl, benzyl, and C₂H₄C₆H₅, thenthe amount of said first recurring unit is greater than the amount ofsaid second recurring unit on a molar basis, and wherein, if said R₂, R₃and R₄ in said first recurring unit together contain a total of 3 carbonatoms, then said first polymer is devoid of hydrophobic recurring units.27. A composition as claimed in claim 17, wherein, if said first polymeris further comprised of a second recurring unit of formula (I) whereinR₁ is H or CH₃, A is O or NH, B is an alkylene or branched alkylene oroxyalkylene group having from 1 to 5 carbons, X is a counterion, and R₂,R₃ or R₄ is selected from the group consisting of C₄-C₁₀ alkyl, benzyl,and C₂H₄C₆H₅, then the amount of said first recurring unit is greaterthan the amount of said second recurring unit on a molar basis.